def banner(text, type=1, width=35):
"""Function to print *text* to output file in a banner of
minimum width *width* and minimum three-line height for
*type* = 1 or one-line height for *type* = 2.
"""
lines = text.split("\n")
max_length = 0
for line in lines:
if len(line) > max_length:
max_length = len(line)
max_length = max([width, max_length])
null = ""
if type == 1:
banner = " //" + null.center(max_length, ">") + "//\n"
for line in lines:
banner += " //" + line.center(max_length) + "//\n"
banner += " //" + null.center(max_length, "<") + "//\n"
if type == 2:
banner = ""
for line in lines:
banner += (" " + line + " ").center(max_length, "=")
psi4.print_out(banner)
def compare_vectors(expected, computed, digits, label):
"""Function to compare two vectors. Prints :py:func:`util.success`
when elements of vector *computed* match elements of vector *expected* to
number of *digits*. Performs a system exit on failure to match symmetry
structure, dimension, or element values. Used in input files in the test suite.
"""
if (expected.nirrep() != computed.nirrep()):
print("\t%s has %d irreps, but %s has %d\n." % (expected.name(), expected.nirrep(), computed.name(), computed.nirrep()))
sys.exit(1)
nirreps = expected.nirrep()
for irrep in range(nirreps):
if(expected.dim(irrep) != computed.dim(irrep)):
print("\tThe reference has %d entries in irrep %d, but the computed vector has %d\n." % (expected.dim(irrep), irrep, computed.dim(irrep)))
sys.exit(1)
dim = expected.dim(irrep)
failed = 0
for entry in range(dim):
if(abs(expected.get(irrep, entry) - computed.get(irrep, entry)) > 10 ** (-digits)):
print("\t%s: computed value (%s) does not match (%s)." % (label, computed.get(irrep, entry), expected.get(irrep, entry)))
failed = 1
break
if(failed):
psi4.print_out("The computed vector\n")
computed.print_out()
psi4.print_out("The reference vector\n")
expected.print_out()
sys.exit(1)
success(label)
def __init__(self, circs):
if circs[5] == '':
msg = """{0}: Method '{1}' with {2} '{3}' and REFERENCE '{4}' not available{5}""".format(*circs)
else:
msg = """{0}: Method '{1}' with {2} '{3}' and REFERENCE '{4}' not directable to QC_MODULE '{5}'""".format(*circs)
PsiException.__init__(self, msg)
self.message = msg
psi4.print_out('\nPsiException: %s\n\n' % (msg))
def compute_energy(self):
uhf = self.uhf
e, nocc, norb, gmo = self.uhf.e, self.uhf.nocc, self.uhf.norb, self.gmo
Ec = 0.0
for i in range(nocc):
for j in range(nocc):
for a in range(nocc, norb):
for b in range(nocc, norb):
Ec += (1/4.0) * gmo[i, j, a, b]**2 / (e[i]+e[j]-e[a]-e[b])
self.E = uhf.E + Ec
psi4.print_out('MP2 E Ec\n')
psi4.print_out(' {:20.15f} {:20.15f}'.format(self.E, Ec))
return Ec
def extract_sowreap_from_output(sowout, quantity, sownum, linkage, allvital=False):
"""Function to examine file *sowout* from a sow/reap distributed job
for formatted line with electronic energy information about index
*sownum* to be used for construction of *quantity* computations as
directed by master input file with *linkage* kwarg. When file *sowout*
is missing or incomplete files, function will either return zero
(*allvital* is ``False``) or terminate (*allvital* is ``True``) since
some sow/reap procedures can produce meaningful results (database)
from an incomplete set of sown files, while others cannot (gradient,
hessian).
"""
E = 0.0
try:
freagent = open('%s.out' % (sowout), 'r')
except IOError:
if allvital:
raise ValidationError('Aborting upon output file \'%s.out\' not found.\n' % (sowout))
else:
ValidationError('Aborting upon output file \'%s.out\' not found.\n' % (sowout))
return 0.0
else:
while True:
line = freagent.readline()
if not line:
if E == 0.0:
if allvital:
raise ValidationError('Aborting upon output file \'%s.out\' has no %s RESULT line.\n' % (sowout, quantity))
else:
ValidationError('Aborting upon output file \'%s.out\' has no %s RESULT line.\n' % (sowout, quantity))
break
s = line.split()
if (len(s) != 0) and (s[0:3] == [quantity, 'RESULT:', 'computation']):
if int(s[3]) != linkage:
raise ValidationError('Output file \'%s.out\' has linkage %s incompatible with master.in linkage %s.'
% (sowout, str(s[3]), str(linkage)))
if s[6] != str(sownum + 1):
raise ValidationError('Output file \'%s.out\' has nominal affiliation %s incompatible with item %s.'
% (sowout, s[6], str(sownum + 1)))
if (s[8:10] == ['electronic', 'energy']):
E = float(s[10])
psi4.print_out('%s RESULT: electronic energy = %20.12f\n' % (quantity, E))
freagent.close()
return E
def fitGeneral(self):
"""Function to perform a general fit of diffuse charges
to wavefunction density.
"""
psi4.print_out(" => Diffuse Charge Fitting (Determines da) <=\n\n")
self.wfn = psi4.wavefunction()
self.Da = self.wfn.Da()
self.basis = self.wfn.basisset()
parser = psi4.Gaussian94BasisSetParser()
self.ribasis = psi4.BasisSet.construct(parser, self.molecule, "DF_BASIS_SCF")
fitter = psi4.DFChargeFitter()
fitter.setPrimary(self.basis)
fitter.setAuxiliary(self.ribasis)
fitter.setD(self.Da)
self.da = fitter.fit()
self.da.scale(2.0)
def compute_energy(self):
"""
Compute the MP2 energy
:return: MP2 energy
"""
ndocc = self.ndocc
nbf = self.nbf
gmo = self.gmo
e = self.e
E = 0.0
for i in range(ndocc):
for j in range(ndocc):
for a in range(ndocc, nbf):
for b in range(ndocc, nbf):
E += gmo[i, a, j, b]*(2*gmo[i, a, j, b] - gmo[i, b, j, a])/\
(e[i] + e[j] - e[a] - e[b])
psi4.print_out('@MP2 correlation energy: {:20.15f}\n'.format(E))
psi4.print_out('@Total MP2 energy: {:20.15f}\n'.format(E + self.ehf))
self.emp2 = E
def _print_nbody_energy(energy_body_dict, header):
psi4.print_out("""\n ==> N-Body: %s energies <==\n\n""" % header)
psi4.print_out(""" n-Body Total Energy [Eh] I.E. [kcal/mol] Delta [kcal/mol]\n""")
previous_e = energy_body_dict[1]
nbody_range = energy_body_dict.keys()
nbody_range.sort()
for n in nbody_range:
delta_e = (energy_body_dict[n] - previous_e)
delta_e_kcal = delta_e * p4const.psi_hartree2kcalmol
int_e_kcal = (energy_body_dict[n] - energy_body_dict[1]) * p4const.psi_hartree2kcalmol
psi4.print_out(""" %4s %20.12f %20.12f %20.12f\n""" %
(n, energy_body_dict[n], int_e_kcal, delta_e_kcal))
previous_e = energy_body_dict[n]
psi4.print_out("\n")
def compute_energy(self):
S = np.matrix(la.block_diag(self.S, self.S))
T = np.matrix(la.block_diag(self.T, self.T))
V = np.matrix(la.block_diag(self.V, self.V))
D = np.matrix(np.zeros((self.nsbf, self.nsbf)))
X = np.matrix(la.inv(la.sqrtm(S)))
h = T + V
E0 = 0
for count in range(self.maxiter):
F = h + self.vu
Ft = X * F * X
e, Ct = la.eigh(Ft)
C = X * np.matrix(Ct)
OC = np.matrix(C[:,:self.nelec])
D = OC*OC.T
self.vu = np.einsum('upvq,qp->uv', self.G, D)
E1 = np.sum((np.array(h) + 0.5 * np.array(self.vu))*np.array(D.T)) + self.V_nuc
psi4.print_out('Iteration {:<d} {:.10f} {:.10f}\n'.format(count, E1, E1-E0))
if abs(E1 - E0) < self.e_convergence:
psi4.print_out('\nFinal HF Energy: {:<5.10f}'.format(E1))
self.C = C
self.epsi = e
self.ehf = E1
break
else:
E0 = E1
else:
psi4.print_out('\n:( Does not converge :(')
def compute_energy(self):
"""
Compute the rhf energy
:return: energy
"""
X = np.matrix(la.inv(la.sqrtm(self.S)))
D = np.matrix(np.zeros((self.nbf, self.nbf)))
h = self.T + self.V
E0 = 0
for count in range(self.maxiter):
F = h + self.vu
Ft = X * F * X
e, Ct = la.eigh(Ft)
C = X * np.matrix(Ct)
DOC = np.matrix(C[:,:self.ndocc])
D = DOC*DOC.T
G = 2*self.g - self.g.swapaxes(2,3)
self.vu = np.einsum('upvq,qp->uv', G, D)
E1 = np.sum((2 * np.array(h) + np.array(self.vu))*np.array(D.T)) + self.V_nuc
psi4.print_out('Iteration {:<d} {:.10f} {:.10f}\n'.format(count, E1, E1-E0))
if abs(E1 - E0) < self.e_convergence:
psi4.print_out('\nFinal Energy: {:<5.10f}'.format(E1))
break
else:
E0 = E1
else:
psi4.print_out('\n:( Does not converge :(')
def fitScf(self):
"""Function to run scf and fit a system of diffuse charges to
resulting density.
"""
basisChanged = psi4.has_option_changed("BASIS")
ribasisChanged = psi4.has_option_changed("DF_BASIS_SCF")
scftypeChanged = psi4.has_option_changed("SCF_TYPE")
basis = psi4.get_option("BASIS")
ribasis = psi4.get_option("DF_BASIS_SCF")
scftype = psi4.get_option("SCF_TYPE")
psi4.print_out(" => Diffuse SCF (Determines Da) <=\n\n")
activate(self.molecule)
psi4.set_global_option("BASIS", self.basisname)
psi4.set_global_option("DF_BASIS_SCF", self.ribasisname)
psi4.set_global_option("SCF_TYPE", "DF")
energy('scf')
psi4.print_out("\n")
self.fitGeneral()
psi4.clean()
psi4.set_global_option("BASIS", basis)
psi4.set_global_option("DF_BASIS_SCF", ribasis)
psi4.set_global_option("SCF_TYPE", scftype)
if not basisChanged:
psi4.revoke_option_changed("BASIS")
if not ribasisChanged:
psi4.revoke_option_changed("DF_BASIS_SCF")
if not scftypeChanged:
psi4.revoke_option_changed("SCF_TYPE")
def compute_energy(self):
"""
Compute the rhf energy
:return: energy
"""
V_nuc, T, S, V, g = self.V_nuc, self.T, self.S, self.V, self.g
nbf, ndocc = self.nbf, self.ndocc
D = np.zeros((self.nbf, self.nbf))
C = np.zeros((self.nbf, self.nbf))
# S^{-1/2}
X = la.inv(la.sqrtm(S)).view(np.matrix)
psi4.print_out('Iter. Energy\n')
scf_form = '{: >3d} {: >20.15f}\n'
i = 0
converged = False
e_old = 0
# Begin SCF iterations
while not converged and i < self.maxiter:
F = self.build_fock(D)
# Transformed Fock matrix to an orthogonal basis
tF = X*F*X
# Diagonalized the transformed Fock matrix
e, tC = la.eigh(tF)
# Convert eigenvectors to AO basis (from orthogonal basis)
C = X*tC
# Form density matrix
D = C[:, :ndocc]*C[:, :ndocc].T
# Compute the energy
E = np.trace((F + T +V)*D) + V_nuc
i += 1
# Check convergence
if abs(E - e_old) < self.e_convergence:
converged = True
e_old = E
psi4.print_out(scf_form.format(i, E))
psi4.print_out('RHF Energy: {:20.15f}\n'.format(E))
self.e = e
self.C = C
self.E = E
return E
def compute_energy(self):
"""
Compute the rhf energy
:return: energy
"""
T, V, h, S, X = self.T, self.V, self.h, self.S, self.X
V_nuc, nocc = self.V_nuc, self.nocc
# Use an empty density guess
D = np.zeros(T.shape)
psi4.print_out('\nIter. Energy\n')
scf_form = '{: >3d} {: >20.15f}\n'
i = 0
converged = False
e_old = 0
# Begin SCF iterations
while not converged and i < self.maxiter:
# build the Fock with the previous density
f = self.build_fock(D)
# Transform the Fock matrix to an orthogonal basis
tf = X*f*X
# Diagonalize the transformed Fock matrix
e, tC = la.eigh(tf)
# Convert eigenvectors to AO basis (from orthogonal basis)
C = X*tC
# Form density matrix
D = C[:, :nocc]*C[:, :nocc].T
# Compute the energy
E = np.trace((h/2 + f/2)*D) + V_nuc
i += 1
# Check convergence
if abs(E - e_old) < self.e_convergence:
converged = True
e_old = E
psi4.print_out(scf_form.format(i, E))
psi4.print_out('RHF Energy: {:20.15f}\n'.format(E))
self.E = E
self.C = C
self.e = e
return E
def compare_matrices(expected, computed, digits, label):
"""Function to compare two matrices. Prints :py:func:`util.success`
when elements of matrix *computed* match elements of matrix *expected* to
number of *digits*. Performs a system exit on failure to match symmetry
structure, dimensions, or element values. Used in input files in the test suite.
"""
if (expected.nirrep() != computed.nirrep()):
print("\t%s has %d irreps, but %s has %d\n." % (expected.name(), expected.nirrep(), computed.name(), computed.nirrep()))
sys.exit(1)
if (expected.symmetry() != computed.symmetry()):
print("\t%s has %d symmetry, but %s has %d\n." % (expected.name(), expected.symmetry(), computed.name(), computed.symmetry()))
sys.exit(1)
nirreps = expected.nirrep()
symmetry = expected.symmetry()
for irrep in range(nirreps):
if(expected.rows(irrep) != computed.rows(irrep)):
print("\t%s has %d rows in irrep %d, but %s has %d\n." % (expected.name(), expected.rows(irrep), irrep, computed.name(), computed.rows(irrep)))
sys.exit(1)
if(expected.cols(irrep ^ symmetry) != computed.cols(irrep ^ symmetry)):
print("\t%s has %d columns in irrep, but %s has %d\n." % (expected.name(), expected.cols(irrep), irrep, computed.name(), computed.cols(irrep)))
sys.exit(1)
rows = expected.rows(irrep)
cols = expected.cols(irrep ^ symmetry)
failed = 0
for row in range(rows):
for col in range(cols):
if(abs(expected.get(irrep, row, col) - computed.get(irrep, row, col)) > 10 ** (-digits)):
print("\t%s: computed value (%s) does not match (%s)." % (label, expected.get(irrep, row, col), computed.get(irrep, row, col)))
failed = 1
break
if(failed):
print("Check your output file for reporting of the matrices.")
psi4.print_out("The Failed Test Matrices\n")
psi4.print_out("Computed Matrix (2nd matrix passed in)\n")
computed.print_out()
psi4.print_out("Expected Matrix (1st matrix passed in)\n")
expected.print_out()
sys.exit(1)
success(label)
def writeCSX(name, **kwargs):
"""function to write the CSX file
"""
if not psi4.get_global_option('WRITE_CSX'):
return
# import csx_api for csx writing
import os
import math
import inspect
#import openbabel
import qcdb
import qcdb.periodictable
import csx2_api as api
lowername = name.lower()
# Make sure the molecule the user provided is the active one
if ('molecule' in kwargs):
activate(kwargs['molecule'])
del kwargs['molecule']
molecule = psi4.get_active_molecule()
molecule.update_geometry()
# Determine the derivative type
calledby = inspect.stack()[1][3]
derdict = {
'energy': 0,
'property': 0,
'gradient': 1,
'optimize': 1,
'frequency': 2,
'frequencies': 2,
'hessian': 2,
}
dertype = derdict[calledby]
hasFreq = False
# Start to write the CSX file
# First grab molecular information and energies from psi4
geom = molecule.save_string_xyz() # OB
atomLine = geom.split('\n') # OB
# general molecular information
atomNum = molecule.natom()
molSym = molecule.schoenflies_symbol()
molCharge = molecule.molecular_charge()
molMulti = molecule.multiplicity()
# energy information
molBasis = psi4.get_global_option('BASIS')
molSpin = psi4.get_global_option('REFERENCE')
molMethod = psi4.get_global_option('WFN')
mol1E = psi4.get_variable('ONE-ELECTRON ENERGY')
mol2E = psi4.get_variable('TWO-ELECTRON ENERGY')
molNE = psi4.get_variable('NUCLEAR REPULSION ENERGY')
molPE = mol1E + mol2E
molEE = psi4.get_variable('CURRENT ENERGY')
# wavefunction information
try:
wfn = kwargs['wfn']
except AttributeError:
pass
if wfn:
molOrbE = wfn.epsilon_a()
molOrbEb = wfn.epsilon_b()
orbNmopi = wfn.nmopi()
orbNsopi = wfn.nsopi()
orbNum = wfn.nmo() if molOrbE else 0
orbSNum = wfn.nso()
molOrb = wfn.Ca()
orbNirrep = wfn.nirrep()
orbAotoso = wfn.aotoso()
orbDoccpi = wfn.doccpi()
orbSoccpi = wfn.soccpi()
basisNbf = wfn.basisset().nbf()
basisDim = psi4.Dimension(1, 'basisDim')
basisDim.__setitem__(0, basisNbf)
wfnRestricted = True
orbE = []
hlist = []
orblist = []
orbOcc = []
molOrbmo = psi4.Matrix('molOrbmo', basisDim, orbNmopi)
molOrbmo.gemm(False, False, 1.0, orbAotoso, molOrb, 0.0)
if molSpin == 'UHF':
wfnRestricted = False
orbEb = []
hlistCb = []
orblistCb = []
orbOccCb = []
molOrbCb = wfn.Cb()
molOrbmoCb = psi4.Matrix('molOrbmoCb', basisDim, orbNmopi)
molOrbmoCb.gemm(False, False, 1.0, orbAotoso, molOrbCb, 0.0)
count = 0
eleExtra = 1 if wfnRestricted else 0
for ih in range(orbNirrep):
for iorb in range(orbNmopi.__getitem__(ih)):
hlist.append(ih)
orblist.append(iorb)
if molOrbE:
orbE.append(molOrbE.get(count))
eleNum = 1 if iorb < (orbDoccpi.__getitem__(ih) + orbSoccpi.__getitem__(ih)) else 0
eleNum += eleExtra if iorb < orbDoccpi.__getitem__(ih) else 0
orbOcc.append(eleNum)
count += 1
orbMos = sorted(zip(orbE, zip(hlist, orblist)))
orbOccString = ' '.join(str(x) for x in sorted(orbOcc, reverse=True))
orbCaString = []
for imos in range(orbNum):
(h, s) = orbMos[imos][1]
orbCa = []
for iso in range(orbSNum):
orbEle = molOrbmo.get(h, iso, s)
orbCa.append(orbEle)
orbCaString.append(' '.join(str(x) for x in orbCa))
orbEString = ' '.join(str(x) for x in sorted(orbE))
# now for beta spin
if not wfnRestricted:
count = 0
for ih in range(orbNirrep):
for iorb in range(orbNmopi.__getitem__(ih)):
hlistCb.append(ih)
orblist.append(iorb)
if molOrbEb:
orbEb.append(molOrbEb.get(count))
eleNum = 1 if iorb < (orbDoccpi.__getitem__(ih) + orbSoccpi.__getitem__(ih)) else 0
if iorb < orbDoccpi.__getitem__(ih):
eleNum += eleExtra
orbOccCb.append(eleNum)
count += 1
orbMosCb = sorted(zip(orbEb, zip(hlist, orblist)))
orbOccCbString = ' '.join(str(x) for x in sorted(orbOccCb, reverse=True))
orbCbString = []
for imos in range(orbNum):
(h, s) = orbMosCb[imos][1]
orbCb = []
for iso in range(orbSNum):
orbEle = molOrbmoCb.get(h, iso, s)
orbCb.append(orbEle)
orbCbString.append(' '.join(str(x) for x in orbCb))
orbEbString = ' '.join(str(x) for x in sorted(orbEb))
# orbColString = ' '.join(str(x) for x in orbCol)
if wfnRestricted:
wfn1 = api.waveFunctionType(
orbitalCount=orbNum,
orbitalOccupancies=orbOccString)
orbe1 = api.stringArrayType(unit='gc:hartree')
orbe1.set_valueOf_(orbEString)
orbs1 = api.orbitalsType()
for iorb in range(orbNum):
orb1 = api.stringArrayType(id=iorb+1)
orb1.set_valueOf_(orbCaString[iorb])
orbs1.add_orbital(orb1)
wfn1.set_orbitals(orbs1)
wfn1.set_orbitalEnergies(orbe1)
else:
wfn1 = api.waveFunctionType(orbitalCount=orbNum)
# alpha electron: 1.5
orbe1 = api.stringArrayType(unit='gc:hartree')
orbe1.set_valueOf_(orbEString)
wfn1.set_alphaOrbitalEnergies(orbe1)
wfn1.set_alphaOrbitalOccupancies(orbOccString)
aorbs1 = api.orbitalsType()
for iorb in range(orbNum):
orb1 = api.stringArrayType(id=iorb+1)
orb1.set_valueOf_(orbCaString[iorb])
aorbs1.add_orbital(orb1)
wfn1.set_alphaOrbitals(aorbs1)
# beta electron: 1.5
orbeb1 = api.stringArrayType(unit='gc:hartree')
orbeb1.set_valueOf_(orbEbString)
wfn1.set_betaOrbitalEnergies(orbeb1)
wfn1.set_betaOrbitalOccupancies(orbOccCbString)
borbs1 = api.orbitalsType()
for iorb in range(orbNum):
orb1 = api.stringArrayType(id=iorb+1)
orb1.set_valueOf_(orbCbString[iorb])
borbs1.add_orbital(orb1)
wfn1.set_betaOrbitals(borbs1)
# frequency information
if dertype == 2:
hasFreq = True
molFreq = psi4.get_frequencies()
molFreqNum = molFreq.dim(0)
frq = []
irInt = []
for ifrq in range(molFreqNum):
frq.append(molFreq.get(ifrq))
irInt.append(0.0)
frqString = ' '.join(str(x) for x in frq)
intString = ' '.join(str(x) for x in irInt)
normMod = psi4.get_normalmodes()
normMdString = []
count = 0
for ifrq in range(molFreqNum):
normM = []
for iatm in range(atomNum):
for ixyz in range(3):
normM.append(normMod.get(count))
count += 1
normMdString.append(' '.join(str(x) for x in normM))
vib1 = api.vibAnalysisType(vibrationCount=molFreqNum)
freq1 = api.stringArrayType(unit="gc:cm-1")
freq1.set_valueOf_(frqString)
vib1.set_frequencies(freq1)
irint1 = api.stringArrayType()
irint1.set_valueOf_(intString)
vib1.set_irIntensities(irint1)
norms1 = api.normalModesType()
for ifrq in range(molFreqNum):
norm1 = api.normalModeType(id=ifrq+1)
norm1.set_valueOf_(normMdString[ifrq])
norms1.add_normalMode(norm1)
vib1.set_normalModes(norms1)
# dipole moment information
molDipoleX = psi4.get_variable('CURRENT DIPOLE X')
molDipoleY = psi4.get_variable('CURRENT DIPOLE Y')
molDipoleZ = psi4.get_variable('CURRENT DIPOLE Z')
molDipoleTot = math.sqrt(
molDipoleX * molDipoleX +
molDipoleY * molDipoleY +
molDipoleZ * molDipoleZ)
prop1 = api.propertiesType()
sprop1 = api.propertyType(
name='dipoleMomentX',
unit='gc:debye')
sprop1.set_valueOf_(molDipoleX)
sprop2 = api.propertyType(
name='dipoleMomentY',
unit='gc:debye')
sprop2.set_valueOf_(molDipoleY)
sprop3 = api.propertyType(
name='dipoleMomentZ',
unit='gc:debye')
sprop3.set_valueOf_(molDipoleZ)
sprop4 = api.propertyType(
name='dipoleMomentAverage',
unit='gc:debye')
sprop4.set_valueOf_(molDipoleTot)
prop1.add_systemProperty(sprop1)
prop1.add_systemProperty(sprop2)
prop1.add_systemProperty(sprop3)
prop1.add_systemProperty(sprop4)
# get the basename for the CSX file
psio = psi4.IO.shared_object()
namespace = psio.get_default_namespace()
#csxfilename = '.'.join([namespace, str(os.getpid()), 'csx'])
csxfilename = os.path.splitext(psi4.outfile_name())[0] + '.csx'
csxfile = open(csxfilename, 'w')
csxVer = psi4.get_global_option('CSX_VERSION')
# Both CSX versions 0 and 1 depended on the procedures table, which in
# turn required the writeCSX function to be in the driver.py file
# itself. Starting with 1.5 (1, to run), this dependence is broken and
# CSX has been shifted into a plugin.
# Start to generate CSX elements
# CSX version 1.5
if csxVer == 2.0:
# import csx1_api as api
cs1 = api.csType(version='2.0') #5')
# molPublication section: 1.5
mp1 = api.mpubType(
title=psi4.get_global_option('PUBLICATIONTITLE'),
abstract=psi4.get_global_option('PUBLICATIONABSTRACT'),
publisher=psi4.get_global_option('PUBLICATIONPUBLISHER'),
status=['PRELIMINARY', 'DRAFT', 'FINAL'].index(psi4.get_global_option('PUBLICATIONSTATUS')),
category=psi4.get_global_option('PUBLICATIONCATEGORY'),
visibility=['PRIVATE', 'PROTECTED', 'PUBLIC'].index(psi4.get_global_option('PUBLICATIONVISIBILITY')),
tags=psi4.get_global_option('PUBLICATIONTAGS'),
key=psi4.get_global_option('PUBLICATIONKEY'))
email = psi4.get_global_option('EMAIL').replace('__', '@')
mp1.add_author(api.authorType(
creator=psi4.get_global_option('CORRESPONDINGAUTHOR'),
type_='gc:CorrespondingAuthor',
organization=psi4.get_global_option('ORGANIZATION'),
email=None if email == '' else email))
#mp1 = api.mpType(
# title='', abstract='', publisher='', status=0, category=2, visibility=0, tags='', key='')
mp1.set_sourcePackage(api.sourcePackageType(name='Psi4', version=psi4.version()))
#mp1.add_author(api.authorType(creator='', type_='cs:corresponding', organization='', email=''))
cs1.set_molecularPublication(mp1)
# molSystem section: 1.5
ms1 = api.msysType(
systemCharge=molCharge,
systemMultiplicity=molMulti, id='s1')
temp1 = api.dataWithUnitsType(unit='gc:kelvin')
temp1.set_valueOf_(0.0) # LAB dispute
ms1.set_systemTemperature(temp1)
mol1 = api.moleculeType(id='m1', atomCount=molecule.natom())
#OBmol1 = api.moleculeType(id='m1', atomCount=atomNum)
#OBobmol1 = openbabel.OBMol()
#OBfor iatm in range(atomNum):
#OB atomField = atomLine[iatm + 1].split()
#OB atmSymbol = atomField[0]
#OB xCoord = float(atomField[1])
#OB yCoord = float(atomField[2])
#OB zCoord = float(atomField[3])
#OB obatm = obmol1.NewAtom()
#OB obatm.SetAtomicNum(qcdb.periodictable.el2z[atmSymbol.upper()])
#OB obatm.SetVector(xCoord, yCoord, zCoord)
#OBobmol1.ConnectTheDots()
#OBobmol1.PerceiveBondOrders()
#OBobmol1.SetTotalSpinMultiplicity(molMulti)
#OBobmol1.SetTotalCharge(molCharge)
#OBconv1 = openbabel.OBConversion()
#OBconv1.SetInAndOutFormats('mol', 'inchi')
#OBconv1.SetOptions('K', conv1.OUTOPTIONS)
#OBinchikey = conv1.WriteString(obmol1)
#OBmol1.set_inchiKey(inchikey.rstrip())
#OBiatm = 0
for at in range(molecule.natom()):
#xCoord1 = api.dataWithUnitsType(unit='cs:angstrom')
#yCoord1 = api.dataWithUnitsType(unit='cs:angstrom')
#zCoord1 = api.dataWithUnitsType(unit='cs:angstrom')
#xCoord1.set_valueOf_(molecule.x(at) * p4const.psi_bohr2angstroms)
#yCoord1.set_valueOf_(molecule.y(at) * p4const.psi_bohr2angstroms)
#zCoord1.set_valueOf_(molecule.z(at) * p4const.psi_bohr2angstroms)
xCoord1 = api.dataWithUnitsType(unit='gc:bohr')
yCoord1 = api.dataWithUnitsType(unit='gc:bohr')
zCoord1 = api.dataWithUnitsType(unit='gc:bohr')
xCoord1.set_valueOf_(molecule.x(at))
yCoord1.set_valueOf_(molecule.y(at))
zCoord1.set_valueOf_(molecule.z(at))
# LAB 8jun2015: not getting masses from OB anymore so now dependent on qc programs
# current proposition is changing API so masses only go into CSX if relevant (e.g., vib)
# same situation as temperature
atm = api.atomType(
id='a' + str(at + 1),
elementSymbol=molecule.symbol(at),
atomMass=molecule.mass(at), # psi4 uses mass of most common isotope; OB uses natural distribution mass
xCoord3D=xCoord1,
yCoord3D=yCoord1,
zCoord3D=zCoord1,
basisSet='bse:' + molBasis,
calculatedAtomCharge=0,
formalAtomCharge=0)
#OBiatm += 1
#OBcoord1 = api.coordinationType()
#OBibond = 0
#OBfor nb_atom in openbabel.OBAtomAtomIter(obatom):
#OB bond = obatom.GetBond(nb_atom)
#OB bond1 = api.bondType(
#OB id1='a' + str(obatom.GetId() + 1),
#OB id2='a' + str(nb_atom.GetId() + 1))
#OB if bond.GetBondOrder() == 1:
#OB bond1.set_valueOf_('single')
#OB elif bond.GetBondOrder() == 2:
#OB bond1.set_valueOf_('double')
#OB elif bond.GetBondOrder() == 3:
#OB bond1.set_valueOf_('triple')
#OB elif bond.GetBondOrder() == 5:
#OB bond1.set_valueOf_('aromatic')
#OB else:
#OB print('wrong bond order')
#OB coord1.add_bond(bond1)
#OB ibond += 1
#OBcoord1.set_bondCount(ibond)
#OBatm.set_coordination(coord1)
mol1.add_atom(atm)
ms1.add_molecule(mol1)
cs1.set_molecularSystem(ms1)
# molCalculation section: 1.5
mc1 = api.mcalType(id='c1')
qm1 = api.qmCalcType()
srs1 = api.srsMethodType()
psivars = psi4.get_variables()
def form_ene(mandatoryPsivars, optionalPsivars={}, excessPsivars={}):
"""
"""
ene = api.energiesType(unit='gc:hartree')
for pv, csx in mandatoryPsivars.iteritems():
term = api.energyType(type_=csx)
term.set_valueOf_(psivars.pop(pv))
ene.add_energy(term)
for pv, csx in optionalPsivars.iteritems():
if pv in psivars:
term = api.energyType(type_=csx)
term.set_valueOf_(psivars.pop(pv))
ene.add_energy(term)
for pv in excessPsivars:
if pv in psivars:
psivars.pop(pv)
return ene
# Reference stage- every calc has one
if 'CCSD TOTAL ENERGY' in psivars or 'CCSD(T) TOTAL ENERGY' in psivars \
or 'CISD TOTAL ENERGY' in psivars or 'FCI TOTAL ENERGY' in psivars \
or 'QCISD TOTAL ENERGY' in psivars or 'QCISD(T) TOTAL ENERGY' in psivars:
mdm1 = api.srsmdMethodType()
# CCSD(T): 1.5
if 'CCSD(T) TOTAL ENERGY' in psivars:
mandatoryPsivars = {
'CCSD(T) CORRELATION ENERGY': 'gc:correlation',
'CCSD(T) TOTAL ENERGY': 'gc:electronic'}
if not all([pv in psivars for pv in mandatoryPsivars.keys()]):
raise CSXError("""Malformed CCSD(T) computation""")
block = api.resultType( # TODO should be pointing to HF for correlation, maybe to MP2 for guess
methodology='gc:normal', # TODO handle dfcc
spinType='gc:' + molSpin, # TODO could have a closed-shell corl mtd atop open-shell scf?
basisSet='bse:' + molBasis)
block.set_energies(form_ene(mandatoryPsivars))
if hasFreq:
block.set_vibrationalAnalysis(vib1)
mdm1.set_ccsd_t(block)
# CCSD: 1.5
elif 'CCSD TOTAL ENERGY' in psivars:
mandatoryPsivars = {
'CCSD CORRELATION ENERGY': 'gc:correlation',
'CCSD TOTAL ENERGY': 'gc:electronic'}
if not all([pv in psivars for pv in mandatoryPsivars.keys()]):
raise CSXError("""Malformed CCSD computation""")
block = api.resultType( # TODO should be pointing to HF for correlation, maybe to MP2 for guess
methodology='gc:normal', # TODO handle dfcc
spinType='gc:' + molSpin, # TODO could have a closed-shell corl mtd atop open-shell scf?
basisSet='bse:' + molBasis)
block.set_energies(form_ene(mandatoryPsivars))
if hasFreq:
block.set_vibrationalAnalysis(vib1)
mdm1.set_ccsd(block)
# CISD: 1.5
elif 'CISD TOTAL ENERGY' in psivars:
mandatoryPsivars = {
'CISD CORRELATION ENERGY': 'gc:correlation',
'CISD TOTAL ENERGY': 'gc:electronic'}
if not all([pv in psivars for pv in mandatoryPsivars.keys()]):
raise CSXError("""Malformed CISD computation""")
block = api.resultType( # TODO should be pointing to HF for correlation, maybe to MP2 for guess
methodology='gc:normal', # TODO handle dfcc
spinType='gc:' + molSpin, # TODO could have a closed-shell corl mtd atop open-shell scf?
basisSet='bse:' + molBasis)
block.set_energies(form_ene(mandatoryPsivars))
if hasFreq:
block.set_vibrationalAnalysis(vib1)
mdm1.set_cisd(block)
# FCI: 1.5
elif 'FCI TOTAL ENERGY' in psivars:
mandatoryPsivars = {
'FCI CORRELATION ENERGY': 'gc:correlation',
'FCI TOTAL ENERGY': 'gc:electronic'}
if not all([pv in psivars for pv in mandatoryPsivars.keys()]):
raise CSXError("""Malformed FCI computation""")
block = api.resultType( # TODO should be pointing to HF for correlation, maybe to MP2 for guess
methodology='gc:normal', # TODO handle dfcc
spinType='gc:' + molSpin, # TODO could have a closed-shell corl mtd atop open-shell scf?
basisSet='bse:' + molBasis)
block.set_energies(form_ene(mandatoryPsivars))
mdm1.set_fci(block)
# QCISD(T): 1.5
elif 'QCISD(T) TOTAL ENERGY' in psivars:
mandatoryPsivars = {
'QCISD(T) CORRELATION ENERGY': 'gc:correlation',
'QCISD(T) TOTAL ENERGY': 'gc:electronic'}
if not all([pv in psivars for pv in mandatoryPsivars.keys()]):
raise CSXError("""Malformed QCISD(T) computation""")
block = api.resultType( # TODO should be pointing to HF for correlation, maybe to MP2 for guess
methodology='gc:normal', # TODO handle dfcc
spinType='gc:' + molSpin, # TODO could have a closed-shell corl mtd atop open-shell scf?
basisSet='bse:' + molBasis)
block.set_energies(form_ene(mandatoryPsivars))
if hasFreq:
block.set_vibrationalAnalysis(vib1)
mdm1.set_qcisd_t(block)
# QCISD: 1.5
elif 'QCISD TOTAL ENERGY' in psivars:
mandatoryPsivars = {
'QCISD CORRELATION ENERGY': 'gc:correlation',
'QCISD TOTAL ENERGY': 'gc:electronic'}
if not all([pv in psivars for pv in mandatoryPsivars.keys()]):
raise CSXError("""Malformed QCISD computation""")
block = api.resultType( # TODO should be pointing to HF for correlation, maybe to MP2 for guess
methodology='gc:normal', # TODO handle dfcc
spinType='gc:' + molSpin, # TODO could have a closed-shell corl mtd atop open-shell scf?
basisSet='bse:' + molBasis)
block.set_energies(form_ene(mandatoryPsivars))
if hasFreq:
block.set_vibrationalAnalysis(vib1)
mdm1.set_qcisd(block)
srs1.set_multipleDeterminant(mdm1)
elif 'DFT TOTAL ENERGY' in psivars or 'HF TOTAL ENERGY' in psivars \
or 'MP2 TOTAL ENERGY' in psivars or 'MP3 TOTAL ENERGY' in psivars \
or 'MP4 TOTAL ENERGY' in psivars:
sdm1 = api.srssdMethodType()
# DFT 1.5
if 'DFT TOTAL ENERGY' in psivars: # TODO robust enough to avoid MP2C, etc.?
mandatoryPsivars = {
'NUCLEAR REPULSION ENERGY': 'gc:nuclearRepulsion',
'DFT FUNCTIONAL TOTAL ENERGY': 'gc:dftFunctional',
'DFT TOTAL ENERGY': 'gc:electronic'}
optionalPsivars = {
'DOUBLE-HYBRID CORRECTION ENERGY': 'gc:doubleHybrid correction',
'DISPERSION CORRECTION ENERGY': 'gc:dispersion correction'}
excessPsivars = [
'MP2 TOTAL ENERGY',
'MP2 CORRELATION ENERGY',
'MP2 SAME-SPIN CORRELATION ENERGY']
if not all([pv in psivars for pv in mandatoryPsivars.keys()]):
raise CSXError("""Malformed DFT computation""")
block = api.resultType(
methodology='gc:normal', # TODO handle dfhf, dfmp
spinType='gc:' + molSpin,
basisSet='bse:' + molBasis,
dftFunctional=name) # TODO this'll need to be exported
block.set_energies(form_ene(mandatoryPsivars, optionalPsivars, excessPsivars))
if wfn:
block.set_waveFunction(wfn1)
if hasFreq:
block.set_vibrationalAnalysis(vib1)
block.set_properties(prop1)
sdm1.set_dft(block)
# post-reference block
# MP4: 1.5
elif 'MP4 TOTAL ENERGY' in psivars:
mandatoryPsivars = {
'MP4 CORRELATION ENERGY': 'gc:correlation',
'MP4 TOTAL ENERGY': 'gc:electronic'}
optionalPsivars = {
'MP4 SAME-SPIN CORRELATION ENERGY': 'gc:sameSpin correlation'}
if not all([pv in psivars for pv in mandatoryPsivars.keys()]):
raise CSXError("""Malformed MP4 computation""")
block = api.resultType( # TODO should be pointing to HF for correlation
methodology='gc:normal', # TODO handle dfmp
spinType='gc:' + molSpin, # TODO could have a closed-shell corl mtd atop open-shell scf?
basisSet='bse:' + molBasis)
block.set_energies(form_ene(mandatoryPsivars, optionalPsivars))
if wfn:
block.set_waveFunction(wfn1)
if hasFreq:
block.set_vibrationalAnalysis(vib1)
block.set_properties(prop1)
sdm1.set_mp4(block)
# MP3: 1.5
elif 'MP3 TOTAL ENERGY' in psivars:
mandatoryPsivars = {
'MP3 CORRELATION ENERGY': 'gc:correlation',
'MP3 TOTAL ENERGY': 'gc:electronic'}
optionalPsivars = {
'MP3 SAME-SPIN CORRELATION ENERGY': 'gc:sameSpin correlation'}
if not all([pv in psivars for pv in mandatoryPsivars.keys()]):
raise CSXError("""Malformed MP3 computation""")
block = api.resultType( # TODO should be pointing to HF for correlation
methodology='gc:normal', # TODO handle dfmp
spinType='gc:' + molSpin, # TODO could have a closed-shell corl mtd atop open-shell scf?
basisSet='bse:' + molBasis)
block.set_energies(form_ene(mandatoryPsivars, optionalPsivars))
if wfn:
block.set_waveFunction(wfn1)
if hasFreq:
block.set_vibrationalAnalysis(vib1)
block.set_properties(prop1)
sdm1.set_mp3(block)
# MP2: 1.5
elif 'MP2 TOTAL ENERGY' in psivars:
mandatoryPsivars = {
'MP2 CORRELATION ENERGY': 'gc:correlation',
'MP2 TOTAL ENERGY': 'gc:electronic'}
optionalPsivars = {
'MP2 SAME-SPIN CORRELATION ENERGY': 'gc:sameSpin correlation'}
if not all([pv in psivars for pv in mandatoryPsivars.keys()]):
raise CSXError("""Malformed MP2 computation""")
block = api.resultType( # TODO should be pointing to HF for correlation
methodology='gc:normal', # TODO handle dfmp
spinType='gc:' + molSpin, # TODO could have a closed-shell corl mtd atop open-shell scf?
basisSet='bse:' + molBasis)
block.set_energies(form_ene(mandatoryPsivars, optionalPsivars))
if wfn:
block.set_waveFunction(wfn1)
if hasFreq:
block.set_vibrationalAnalysis(vib1)
block.set_properties(prop1)
sdm1.set_mp2(block)
# SCF: 1.5
elif 'HF TOTAL ENERGY' in psivars:
mandatoryPsivars = {
'NUCLEAR REPULSION ENERGY': 'gc:nuclearRepulsion',
'HF TOTAL ENERGY': 'gc:electronic'}
if not all([pv in psivars for pv in mandatoryPsivars.keys()]):
raise CSXError("""Malformed HF computation""")
block = api.resultType(
methodology='gc:normal', # TODO handle dfhf, dfmp
spinType='gc:' + molSpin,
basisSet='bse:' + molBasis)
block.set_energies(form_ene(mandatoryPsivars))
if wfn:
block.set_waveFunction(wfn1)
if hasFreq:
block.set_vibrationalAnalysis(vib1)
block.set_properties(prop1)
sdm1.set_abinitioScf(block)
else:
psi4.print_out("""\nCSX version {0} does not support """
"""method {1} for {2}\n""".format(
csxVer, lowername, 'energies'))
srs1.set_singleDeterminant(sdm1)
#print('CSX not harvesting: ', ', '.join(psivars))
qm1.set_singleReferenceState(srs1)
mc1.set_quantumMechanics(qm1)
cs1.set_molecularCalculation(mc1)
else:
print('The future CSX file is here')
csxfile.write('<?xml version="1.0" encoding="UTF-8"?>\n')
cs1.export(csxfile, 0)
csxfile.close()
def auto_fragments(**kwargs):
r"""Detects fragments if the user does not supply them.
Currently only used for the WebMO implementation of SAPT.
:returns: :ref:`Molecule<sec:psimod_Molecule>`) |w--w| fragmented molecule.
:type molecule: :ref:`molecule <op_py_molecule>`
:param molecule: ``h2o`` || etc.
The target molecule, if not the last molecule defined.
:examples:
>>> # [1] replicates with cbs() the simple model chemistry scf/cc-pVDZ: set basis cc-pVDZ energy('scf')
>>> molecule mol {\nH 0.0 0.0 0.0\nH 2.0 0.0 0.0\nF 0.0 1.0 0.0\nF 2.0 1.0 0.0\n}
>>> print mol.nfragments() # 1
>>> fragmol = auto_fragments()
>>> print fragmol.nfragments() # 2
"""
# Make sure the molecule the user provided is the active one
molecule = kwargs.pop('molecule', psi4.get_active_molecule())
molecule.update_geometry()
molname = molecule.name()
geom = molecule.save_string_xyz()
numatoms = molecule.natom()
VdW = [1.2, 1.7, 1.5, 1.55, 1.52, 1.9, 1.85, 1.8]
symbol = list(range(numatoms))
X = [0.0] * numatoms
Y = [0.0] * numatoms
Z = [0.0] * numatoms
Queue = []
White = []
Black = []
F = geom.split('\n')
for f in range(numatoms):
A = F[f + 1].split()
symbol[f] = A[0]
X[f] = float(A[1])
Y[f] = float(A[2])
Z[f] = float(A[3])
White.append(f)
Fragment = [[] for i in range(numatoms)] # stores fragments
start = 0 # starts with the first atom in the list
Queue.append(start)
White.remove(start)
frag = 0
while((len(White) > 0) or (len(Queue) > 0)): # Iterates to the next fragment
while(len(Queue) > 0): # BFS within a fragment
for u in Queue: # find all nearest Neighbors
# (still coloured white) to vertex u
for i in White:
Distance = math.sqrt((X[i] - X[u]) * (X[i] - X[u]) +
(Y[i] - Y[u]) * (Y[i] - Y[u]) +
(Z[i] - Z[u]) * (Z[i] - Z[u]))
if Distance < _autofragment_convert(u, symbol) + _autofragment_convert(i, symbol):
Queue.append(i) # if you find you, put it in the que
White.remove(i) # and remove it from the untouched list
Queue.remove(u) # remove focus from Queue
Black.append(u)
Fragment[frag].append(int(u + 1)) # add to group (adding 1 to start
# list at one instead of zero)
if(len(White) != 0): # cant move White->Queue if no more exist
Queue.append(White[0])
White.remove(White[0])
frag += 1
new_geom = """\n"""
for i in Fragment[0]:
new_geom = new_geom + F[i].lstrip() + """\n"""
new_geom = new_geom + """--\n"""
for j in Fragment[1]:
new_geom = new_geom + F[j].lstrip() + """\n"""
new_geom = new_geom + """units angstrom\n"""
moleculenew = psi4.Molecule.create_molecule_from_string(new_geom)
moleculenew.set_name(molname)
moleculenew.update_geometry()
moleculenew.print_cluster()
psi4.print_out(""" Exiting auto_fragments\n""")
return moleculenew
def __init__(self, msg):
PsiException.__init__(self, msg)
self.message = msg
psi4.print_out('\nCSXException: %s\n\n' % (msg))
def run_roa(name, **kwargs):
# Get list of omega values -> Make sure we only have one wavelength
# Catch this now before any real work gets done
omega = psi4.get_option('CCRESPONSE','OMEGA')
if len(omega) > 2:
raise Exception('ROA scattering can only be performed for one wavelength.')
else:
pass
psi4.print_out('Running ROA computation. Subdirectories for each '
'required displaced geometry have been created.\n\n')
### Initialize database
db = shelve.open('database',writeback=True)
if 'inputs_generated' not in db:
initialize_database(db)
### Generate input files
if not db['inputs_generated']:
generate_inputs(name, db)
db['inputs_generated'] = True
### If 'serial' calculation, proceed with subdir execution
### Check job status
if db['inputs_generated'] and not db['jobs_complete']:
print('Checking status')
roa_stat(db)
for job,status in db['job_status'].items():
print("{} --> {}".format(job,status))
### Compute ROA Scattering
if db['jobs_complete']:
# SAVE this for when multiple wavelengths works
# # Get list of omega values
# omega = psi4.get_option('CCRESPONSE','OMEGA')
# if len(omega) > 1:
# units = copy.copy(omega[-1])
# omega.pop()
# else:
# units = 'atomic'
# wavelength = copy.copy(omega[0])
# # Set up units for scatter.cc
# if units == 'NM':
# wavelength = (psi_c * psi_h * 1*(10**-9))/(wavelength * psi_hartree2J)
# if units == 'HZ':
# wavelength = wavelength * psi_h / psi_hartree2J
# if units == 'EV':
# wavelength = wavelength / psi_hartree2ev
# if units == 'atomic':
# pass
# Initialize tensor lists
dip_polar_list = []
opt_rot_list = []
dip_quad_polar_list = []
gauge_list = []
make_gauge_list(gauge_list)
# Gather data
synthesize_dipole_polar(db,dip_polar_list)
synthesize_opt_rot(db,opt_rot_list)
synthesize_dip_quad_polar(db,dip_quad_polar_list)
# Compute Scattering
# Run new function (src/bin/ccresponse/scatter.cc)
psi4.print_out('Running scatter function')
step = psi4.get_local_option('FINDIF','DISP_SIZE')
for gauge in opt_rot_list:
g_idx = opt_rot_list.index(gauge)
# print('\n\n----------------------------------------------------------------------')
# print('\t%%%%%%%%%% {} %%%%%%%%%%'.format(gauge_list[g_idx]))
# print('----------------------------------------------------------------------\n\n')
psi4.print_out('\n\n----------------------------------------------------------------------\n')
psi4.print_out('\t%%%%%%%%%% {} %%%%%%%%%%\n'.format(gauge_list[g_idx]))
psi4.print_out('----------------------------------------------------------------------\n\n')
print('roa.py:85 I am not being passed a molecule, grabbing from global :(')
psi4.scatter(psi4.get_active_molecule(), step, dip_polar_list, gauge, dip_quad_polar_list)
db.close()
def process_input(raw_input, print_level=1):
"""Function to preprocess *raw input*, the text of the input file, then
parse it, validate it for format, and convert it into legitimate Python.
*raw_input* is printed to the output file unless *print_level* =0. Does
a series of regular expression filters, where the matching portion of the
input is replaced by the output of the corresponding function (in this
module) call. Returns a string concatenating module import lines, a copy
of the user's .psi4rc files, a setting of the scratch directory, a dummy
molecule, and the processed *raw_input*.
"""
# Check if the infile is actually an outfile (yeah we did)
psi4_id = re.compile(r'PSI4: An Open-Source Ab Initio Electronic Structure Package')
if (re.search(psi4_id, raw_input)):
input_lines = raw_input.split("\n")
input_re = re.compile(r'^\s*?\=\=> Input File <\=\=')
input_start = -1
for line_count in range(len(input_lines)):
line = input_lines[line_count]
if re.match(input_re, line):
input_start = line_count + 3
break
stop_re = re.compile(r'^-{74}')
input_stop = -1
for line_count in range(input_start, len(input_lines)):
line = input_lines[line_count]
if re.match(stop_re, line):
input_stop = line_count
break
if (input_start == -1 or input_stop == -1):
print('Cannot extract infile from outfile.')
sys.exit(1)
raw_input = '\n'.join(input_lines[input_start:input_stop])
raw_input += '\n'
# Echo the infile on the outfile
if print_level > 0:
psi4.print_out("\n ==> Input File <==\n\n")
psi4.print_out("--------------------------------------------------------------------------\n")
psi4.print_out(raw_input)
psi4.print_out("--------------------------------------------------------------------------\n")
psi4.flush_outfile()
#NOTE: If adding mulitline data to the preprocessor, use ONLY the following syntax:
# function [objname] { ... }
# which has the regex capture group:
#
# r'^(\s*?)FUNCTION\s*(\w*?)\s*\{(.*?)\}', re.MULTILINE | re.DOTALL | re.IGNORECASE
#
# your function is in capture group #1
# your objname is in capture group #2
# your data is in capture group #3
# Nuke all comments
comment = re.compile(r'[^\\]#.*')
temp = re.sub(comment, '', raw_input)
# Now, nuke any escapes from comment lines
comment = re.compile(r'\\#')
temp = re.sub(comment, '#', temp)
# Check the brackets and parentheses match up, as long as this is not a pickle input file
if not re.search(r'pickle_kw', temp):
check_parentheses_and_brackets(temp, 1)
# First, remove everything from lines containing only spaces
blankline = re.compile(r'^\s*$')
temp = re.sub(blankline, '', temp, re.MULTILINE)
# Look for things like
# set matrix [
# [ 1, 2 ],
# [ 3, 4 ]
# ]
# and put them on a single line
temp = process_multiline_arrays(temp)
# Process all "set name? { ... }"
set_commands = re.compile(r'^(\s*?)set\s*([-,\w]*?)[\s=]*\{(.*?)\}',
re.MULTILINE | re.DOTALL | re.IGNORECASE)
temp = re.sub(set_commands, process_set_commands, temp)
# Process all individual "set (module_list) key {[value_list] or $value or value}"
# N.B. We have to be careful here, because \s matches \n, leading to potential problems
# with undesired multiline matches. Better the double-negative [^\S\n] instead, which
# will match any space, tab, etc., except a newline
set_command = re.compile(r'^(\s*?)set\s+(?:([-,\w]+)[^\S\n]+)?(\w+)(?:[^\S\n]|=)+((\[.*\])|(\$?[-+,*()\.\w]+))\s*$',
re.MULTILINE | re.IGNORECASE)
temp = re.sub(set_command, process_set_command, temp)
# Process "molecule name? { ... }"
molecule = re.compile(r'^(\s*?)molecule[=\s]*(\w*?)\s*\{(.*?)\}',
re.MULTILINE | re.DOTALL | re.IGNORECASE)
temp = re.sub(molecule, process_molecule_command, temp)
# Process "external name? { ... }"
external = re.compile(r'^(\s*?)external[=\s]*(\w*?)\s*\{(.*?)\}',
re.MULTILINE | re.DOTALL | re.IGNORECASE)
temp = re.sub(external, process_external_command, temp)
# Process "pcm name? { ... }"
pcm = re.compile(r'^(\s*?)pcm[=\s]*(\w*?)\s*\{(.*?)^\}',
re.MULTILINE | re.DOTALL | re.IGNORECASE)
temp = re.sub(pcm, process_pcm_command, temp)
# Then remove repeated newlines
multiplenewlines = re.compile(r'\n+')
temp = re.sub(multiplenewlines, '\n', temp)
# Process " extract"
extract = re.compile(r'(\s*?)(\w+)\s*=\s*\w+\.extract_subsets.*',
re.IGNORECASE)
temp = re.sub(extract, process_extract_command, temp)
# Process "print" and transform it to "psi4.print_out()"
#print_string = re.compile(r'(\s*?)print\s+(.*)', re.IGNORECASE)
#temp = re.sub(print_string, process_print_command, temp)
# Process "memory ... "
memory_string = re.compile(r'(\s*?)memory\s+([+-]?\d*\.?\d+)\s+([KMG]i?B)',
re.IGNORECASE)
temp = re.sub(memory_string, process_memory_command, temp)
# Process "basis file ... "
basis_file = re.compile(r'(\s*?)basis\s+file\s*(\b.*\b)\s*$',
re.MULTILINE | re.IGNORECASE)
temp = re.sub(basis_file, process_basis_file, temp)
# Process "basis name { ... }"
basis_block = re.compile(r'(\s*?)basis[=\s]*\{(.*?)\}',
re.MULTILINE | re.DOTALL | re.IGNORECASE)
temp = re.sub(basis_block, process_basis_block, temp)
# Process "basis file ... "
file_pid = re.compile(r'(\s*?)filename\s*(\b.*\b)\s*$',
re.MULTILINE | re.IGNORECASE)
temp = re.sub(file_pid, process_filename, temp)
# imports
imports = 'from psi4 import *\n'
imports += 'from p4const import *\n'
imports += 'from p4util import *\n'
imports += 'from molutil import *\n'
imports += 'from driver import *\n'
imports += 'from wrappers import *\n'
imports += 'from gaussian_n import *\n'
imports += 'from aliases import *\n'
imports += 'from functional import *\n'
imports += 'from qmmm import *\n'
imports += 'psi4_io = psi4.IOManager.shared_object()\n'
# psirc (a baby PSIthon script that might live in ~/.psi4rc)
psirc = ''
homedir = os.path.expanduser('~')
psirc_file = homedir + '/.psi4rc'
if os.path.isfile(psirc_file):
fh = open(psirc_file)
psirc = fh.read()
fh.close()
# Override scratch directory if user specified via env_var
scratch = ''
scratch_env = psi4.Process.environment['PSI_SCRATCH']
if len(scratch_env):
scratch += 'psi4_io.set_default_path("%s")\n' % (scratch_env)
blank_mol = 'geometry("""\n'
blank_mol += '0 1\nH\nH 1 0.74\n'
blank_mol += '""","blank_molecule_psi4_yo")\n'
temp = imports + psirc + scratch + blank_mol + temp
return temp
def _nbody_gufunc(func, method_string, **kwargs):
"""
Computes the nbody interaction energy, gradient, or Hessian depending on input.
Parameters
----------
func : python function
Python function that accepts method_string and a molecule and returns a energy, gradient, or Hessian.
method_string : str
Lowername to be passed to function
molecule : psi4.Molecule (default: Global Molecule)
Molecule to use in all computations
return_wfn : bool (default: False)
Return a wavefunction or not
bsse_type : str or list (default: None, this function is not called)
Type of BSSE correction to compute: CP, NoCP, or VMFC. The first in this list is returned by this function.
max_nbody : int
Maximum n-body to compute, cannot exceede the number of fragments in the moleucle
ptype : str
Type of the procedure passed in
return_total_data : bool (default: False)
If True returns the total data (energy/gradient/etc) of the system otherwise returns interaction data
Returns
-------
data : return type of func
The interaction data
wfn : psi4.Wavefunction (optional)
A wavefunction with energy/gradient/hessian set appropriotely. This wavefunction also contains
Notes
-----
This is a generalized univeral function for compute interaction quantities.
Examples
--------
"""
### ==> Parse some kwargs <==
kwargs = p4util.kwargs_lower(kwargs)
return_wfn = kwargs.pop('return_wfn', False)
ptype = kwargs.pop('ptype', None)
return_total_data = kwargs.pop('return_total_data', False)
molecule = kwargs.pop('molecule', psi4.get_active_molecule())
molecule.update_geometry()
psi4.clean_variables()
if ptype not in ['energy', 'gradient', 'hessian']:
raise ValidationError("""N-Body driver: The ptype '%s' is not regonized.""" % ptype)
# Figure out BSSE types
do_cp = False
do_nocp = False
do_vmfc = False
return_method = False
# Must be passed bsse_type
bsse_type_list = kwargs.pop('bsse_type')
if bsse_type_list is None:
raise ValidationError("N-Body GUFunc: Must pass a bsse_type")
if not isinstance(bsse_type_list, list):
bsse_type_list = [bsse_type_list]
for num, btype in enumerate(bsse_type_list):
if btype.lower() == 'cp':
do_cp = True
if (num == 0): return_method = 'cp'
elif btype.lower() == 'nocp':
do_nocp = True
if (num == 0): return_method = 'nocp'
elif btype.lower() == 'vmfc':
do_vmfc = True
if (num == 0): return_method = 'vmfc'
else:
raise ValidationError("N-Body GUFunc: bsse_type '%s' is not recognized" % btype.lower())
max_nbody = kwargs.get('max_nbody', -1)
max_frag = molecule.nfragments()
if max_nbody == -1:
max_nbody = molecule.nfragments()
else:
max_nbody = min(max_nbody, max_frag)
# What levels do we need?
nbody_range = range(1, max_nbody + 1)
fragment_range = range(1, max_frag + 1)
# If we are doing CP lets save them integrals
if 'cp' in bsse_type_list and (len(bsse_type_list) == 1):
# Set to save RI integrals for repeated full-basis computations
ri_ints_io = psi4.get_global_option('DF_INTS_IO')
# inquire if above at all applies to dfmp2 or just scf
psi4.set_global_option('DF_INTS_IO', 'SAVE')
psioh = psi4.IOManager.shared_object()
psioh.set_specific_retention(97, True)
bsse_str = bsse_type_list[0]
if len(bsse_type_list) >1:
bsse_str = str(bsse_type_list)
psi4.print_out("\n\n")
psi4.print_out(" ===> N-Body Interaction Abacus <===\n")
psi4.print_out(" BSSE Treatment: %s\n" % bsse_str)
cp_compute_list = {x:set() for x in nbody_range}
nocp_compute_list = {x:set() for x in nbody_range}
vmfc_compute_list = {x:set() for x in nbody_range}
vmfc_level_list = {x:set() for x in nbody_range} # Need to sum something slightly different
# Build up compute sets
if do_cp:
# Everything is in dimer basis
basis_tuple = tuple(fragment_range)
for nbody in nbody_range:
for x in it.combinations(fragment_range, nbody):
cp_compute_list[nbody].add( (x, basis_tuple) )
if do_nocp:
# Everything in monomer basis
for nbody in nbody_range:
for x in it.combinations(fragment_range, nbody):
nocp_compute_list[nbody].add( (x, x) )
if do_vmfc:
# Like a CP for all combinations of pairs or greater
for nbody in nbody_range:
for cp_combos in it.combinations(fragment_range, nbody):
basis_tuple = tuple(cp_combos)
for interior_nbody in nbody_range:
for x in it.combinations(cp_combos, interior_nbody):
combo_tuple = (x, basis_tuple)
vmfc_compute_list[interior_nbody].add( combo_tuple )
vmfc_level_list[len(basis_tuple)].add( combo_tuple )
# Build a comprehensive compute_range
compute_list = {x:set() for x in nbody_range}
for n in nbody_range:
compute_list[n] |= cp_compute_list[n]
compute_list[n] |= nocp_compute_list[n]
compute_list[n] |= vmfc_compute_list[n]
psi4.print_out(" Number of %d-body computations: %d\n" % (n, len(compute_list[n])))
# Build size and slices dictionaries
fragment_size_dict = {frag: molecule.extract_subsets(frag).natom() for
frag in range(1, max_frag+1)}
start = 0
fragment_slice_dict = {}
for k, v in fragment_size_dict.items():
fragment_slice_dict[k] = slice(start, start + v)
start += v
molecule_total_atoms = sum(fragment_size_dict.values())
# Now compute the energies
energies_dict = {}
ptype_dict = {}
for n in compute_list.keys():
psi4.print_out("\n ==> N-Body: Now computing %d-body complexes <==\n\n" % n)
print("\n ==> N-Body: Now computing %d-body complexes <==\n" % n)
total = len(compute_list[n])
for num, pair in enumerate(compute_list[n]):
psi4.print_out("\n N-Body: Computing complex (%d/%d) with fragments %s in the basis of fragments %s.\n\n" %
(num + 1, total, str(pair[0]), str(pair[1])))
ghost = list(set(pair[1]) - set(pair[0]))
current_mol = molecule.extract_subsets(list(pair[0]), ghost)
ptype_dict[pair] = func(method_string, molecule=current_mol, **kwargs)
energies_dict[pair] = psi4.get_variable("CURRENT ENERGY")
psi4.print_out("\n N-Body: Complex Energy (fragments = %s, basis = %s: %20.14f)\n" %
(str(pair[0]), str(pair[1]), energies_dict[pair]))
if 'cp' in bsse_type_list and (len(bsse_type_list) == 1):
psi4.set_global_option('DF_INTS_IO', 'LOAD')
psi4.clean()
# Final dictionaries
cp_energy_by_level = {n: 0.0 for n in nbody_range}
nocp_energy_by_level = {n: 0.0 for n in nbody_range}
cp_energy_body_dict = {n: 0.0 for n in nbody_range}
nocp_energy_body_dict = {n: 0.0 for n in nbody_range}
vmfc_energy_body_dict = {n: 0.0 for n in nbody_range}
# Build out ptype dictionaries if needed
if ptype != 'energy':
if ptype == 'gradient':
arr_shape = (molecule_total_atoms, 3)
elif ptype == 'hessian':
arr_shape = (molecule_total_atoms * 3, molecule_total_atoms * 3)
else:
raise KeyError("N-Body: ptype '%s' not recognized" % ptype)
cp_ptype_by_level = {n: np.zeros(arr_shape) for n in nbody_range}
nocp_ptype_by_level = {n: np.zeros(arr_shape) for n in nbody_range}
cp_ptype_body_dict = {n: np.zeros(arr_shape) for n in nbody_range}
nocp_ptype_body_dict = {n: np.zeros(arr_shape) for n in nbody_range}
vmfc_ptype_body_dict = {n: np.zeros(arr_shape) for n in nbody_range}
else:
cp_ptype_by_level, cp_ptype_body_dict = None, None
nocp_ptype_by_level, nocp_ptype_body_dict = None, None
vmfc_ptype_by_level= None
# Sum up all of the levels
for n in nbody_range:
# Energy
cp_energy_by_level[n] = sum(energies_dict[v] for v in cp_compute_list[n])
nocp_energy_by_level[n] = sum(energies_dict[v] for v in nocp_compute_list[n])
# Special vmfc case
if n > 1:
vmfc_energy_body_dict[n] = vmfc_energy_body_dict[n - 1]
for tup in vmfc_level_list[n]:
vmfc_energy_body_dict[n] += ((-1) ** (n - len(tup[0]))) * energies_dict[tup]
# Do ptype
if ptype != 'energy':
_sum_cluster_ptype_data(ptype, ptype_dict, cp_compute_list[n],
fragment_slice_dict, fragment_size_dict,
cp_ptype_by_level[n])
_sum_cluster_ptype_data(ptype, ptype_dict, nocp_compute_list[n],
fragment_slice_dict, fragment_size_dict,
nocp_ptype_by_level[n])
_sum_cluster_ptype_data(ptype, ptype_dict, vmfc_level_list[n],
fragment_slice_dict, fragment_size_dict,
vmfc_ptype_by_level[n], vmfc=True)
# Compute cp energy and ptype
if do_cp:
for n in nbody_range:
if n == max_frag:
cp_energy_body_dict[n] = cp_energy_by_level[n]
if ptype != 'energy':
cp_ptype_body_dict[n][:] = cp_ptype_by_level[n]
continue
for k in range(1, n + 1):
take_nk = nCr(max_frag - k - 1, n - k)
sign = ((-1) ** (n - k))
value = cp_energy_by_level[k]
cp_energy_body_dict[n] += take_nk * sign * value
if ptype != 'energy':
value = cp_ptype_by_level[k]
cp_ptype_body_dict[n] += take_nk * sign * value
_print_nbody_energy(cp_energy_body_dict, "Counterpoise Corrected (CP)")
cp_interaction_energy = cp_energy_body_dict[max_nbody] - cp_energy_body_dict[1]
psi4.set_variable('Counterpoise Corrected Total Energy', cp_energy_body_dict[max_nbody])
psi4.set_variable('Counterpoise Corrected Interaction Energy', cp_interaction_energy)
for n in nbody_range[1:]:
var_key = 'CP-CORRECTED %d-BODY INTERACTION ENERGY' % n
psi4.set_variable(var_key, cp_energy_body_dict[n] - cp_energy_body_dict[1])
# Compute nocp energy and ptype
if do_nocp:
for n in nbody_range:
if n == max_frag:
nocp_energy_body_dict[n] = nocp_energy_by_level[n]
if ptype != 'energy':
nocp_ptype_body_dict[n][:] = nocp_ptype_by_level[n]
continue
for k in range(1, n + 1):
take_nk = nCr(max_frag - k - 1, n - k)
sign = ((-1) ** (n - k))
value = nocp_energy_by_level[k]
nocp_energy_body_dict[n] += take_nk * sign * value
if ptype != 'energy':
value = nocp_ptype_by_level[k]
nocp_ptype_body_dict[n] += take_nk * sign * value
_print_nbody_energy(nocp_energy_body_dict, "Non-Counterpoise Corrected (NoCP)")
nocp_interaction_energy = nocp_energy_body_dict[max_nbody] - nocp_energy_body_dict[1]
psi4.set_variable('Non-Counterpoise Corrected Total Energy', nocp_energy_body_dict[max_nbody])
psi4.set_variable('Non-Counterpoise Corrected Interaction Energy', nocp_interaction_energy)
for n in nbody_range[1:]:
var_key = 'NOCP-CORRECTED %d-BODY INTERACTION ENERGY' % n
psi4.set_variable(var_key, nocp_energy_body_dict[n] - nocp_energy_body_dict[1])
# Compute vmfc energy and ptype
if do_vmfc:
_print_nbody_energy(vmfc_energy_body_dict, "Valiron-Mayer Function Couterpoise (VMFC)")
vmfc_interaction_energy = vmfc_energy_body_dict[max_nbody] - vmfc_energy_body_dict[1]
psi4.set_variable('Valiron-Mayer Function Couterpoise Total Energy', vmfc_energy_body_dict[max_nbody])
psi4.set_variable('Valiron-Mayer Function Couterpoise Interaction Energy', vmfc_interaction_energy)
for n in nbody_range[1:]:
var_key = 'VMFC-CORRECTED %d-BODY INTERACTION ENERGY' % n
psi4.set_variable(var_key, vmfc_energy_body_dict[n] - vmfc_energy_body_dict[1])
if return_method == 'cp':
ptype_body_dict = cp_ptype_body_dict
energy_body_dict = cp_energy_body_dict
elif return_method == 'nocp':
ptype_body_dict = nocp_ptype_body_dict
energy_body_dict = nocp_energy_body_dict
elif return_method == 'vmfc':
ptype_body_dict = vmfc_ptype_body_dict
energy_body_dict = vmfc_energy_body_dict
else:
raise ValidationError("N-Body Wrapper: Invalid return type. Should never be here, please post this error on github.")
# Figure out and build return types
if return_total_data:
ret_energy = energy_body_dict[max_nbody]
else:
ret_energy = energy_body_dict[max_nbody]
ret_energy -= energy_body_dict[1]
if ptype != 'energy':
if return_total_data:
np_final_ptype = ptype_body_dict[max_nbody].copy()
else:
np_final_ptype = ptype_body_dict[max_nbody].copy()
np_final_ptype -= ptype_body_dict[1]
ret_ptype = psi4.Matrix(*np_cp_final_ptype.shape)
ret_ptype_view = np.asarray(final_ptype)
ret_ptype_view[:] = np_final_ptype
else:
ret_ptype = ret_energy
# Build and set a wavefunction
wfn = psi4.new_wavefunction(molecule, 'sto-3g')
wfn.nbody_energy = energies_dict
wfn.nbody_ptype = ptype_dict
wfn.nbody_body_energy = energy_body_dict
wfn.nbody_body_ptype = ptype_body_dict
if ptype == 'gradient':
wfn.set_gradient(ret_ptype)
elif ptype == 'hessian':
wfn.set_hessian(ret_ptype)
psi4.set_variable("CURRENT ENERGY", ret_energy)
if return_wfn:
return (ret_ptype, wfn)
else:
return ret_ptype
def ip_fitting(molecule, omega_l, omega_r, **kwargs):
kwargs = p4util.kwargs_lower(kwargs)
# By default, zero the omega to 3 digits
omega_tol = kwargs.get('omega_tolerance', 1.0E-3)
# By default, do up to twenty iterations
maxiter = kwargs.get('maxiter', 20)
# By default, do not read previous 180 orbitals file
read = False
read180 = ''
if 'read' in kwargs:
read = True
read180 = kwargs['read']
# The molecule is required, and should be the neutral species
molecule.update_geometry()
charge0 = molecule.molecular_charge()
mult0 = molecule.multiplicity()
# How many electrons are there?
N = 0
for A in range(molecule.natom()):
N += molecule.Z(A)
N -= charge0
N = int(N)
Nb = int((N - mult0 + 1) / 2)
Na = int(N - Nb)
# Work in the ot namespace for this procedure
psi4.IO.set_default_namespace("ot")
# Burn in to determine orbital eigenvalues
if read:
psi4.set_global_option("GUESS", "READ")
copy_file_to_scratch(read180, 'psi', 'ot', 180)
old_guess = psi4.get_global_option("GUESS")
psi4.set_global_option("DF_INTS_IO", "SAVE")
psi4.print_out("""\n\t==> IP Fitting SCF: Burn-in <==\n""")
E, wfn = energy('scf', return_wfn=True, molecule=molecule, **kwargs)
psi4.set_global_option("DF_INTS_IO", "LOAD")
# Determine H**O, to determine mult1
eps_a = wfn.epsilon_a()
eps_b = wfn.epsilon_b()
if Na == Nb:
H**O = -Nb
elif Nb == 0:
H**O = Na
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if E_a >= E_b:
H**O = Na
else:
H**O = -Nb
Na1 = Na
Nb1 = Nb
if H**O > 0:
Na1 = Na1 - 1
else:
Nb1 = Nb1 - 1
charge1 = charge0 + 1
mult1 = Na1 - Nb1 + 1
omegas = []
E0s = []
E1s = []
kIPs = []
IPs = []
types = []
# Right endpoint
psi4.set_global_option('DFT_OMEGA', omega_r)
# Neutral
if read:
psi4.set_global_option("GUESS", "READ")
p4util.copy_file_to_scratch(read180, 'psi', 'ot', 180)
molecule.set_molecular_charge(charge0)
molecule.set_multiplicity(mult0)
psi4.print_out("""\n\t==> IP Fitting SCF: Neutral, Right Endpoint <==\n""")
E0r, wfn = energy('scf', return_wfn=True, molecule=molecule, **kwargs)
eps_a = wfn.epsilon_a()
eps_b = wfn.epsilon_b()
E_HOMO = 0.0
if Nb == 0:
E_HOMO = eps_a[int(Na - 1)]
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if E_a >= E_b:
E_HOMO = E_a
else:
E_HOMO = E_b
E_HOMOr = E_HOMO
psi4.IO.change_file_namespace(180, "ot", "neutral")
# Cation
if read:
psi4.set_global_option("GUESS", "READ")
p4util.copy_file_to_scratch(read180, 'psi', 'ot', 180)
molecule.set_molecular_charge(charge1)
molecule.set_multiplicity(mult1)
psi4.print_out("""\n\t==> IP Fitting SCF: Cation, Right Endpoint <==\n""")
E1r = energy('scf', molecule=molecule, **kwargs)
psi4.IO.change_file_namespace(180, "ot", "cation")
IPr = E1r - E0r
kIPr = -E_HOMOr
delta_r = IPr - kIPr
if IPr > kIPr:
message = (
"""\n***IP Fitting Error: Right Omega limit should have kIP > IP"""
)
raise ValidationError(message)
omegas.append(omega_r)
types.append('Right Limit')
E0s.append(E0r)
E1s.append(E1r)
IPs.append(IPr)
kIPs.append(kIPr)
# Use previous orbitals from here out
psi4.set_global_option("GUESS", "READ")
# Left endpoint
psi4.set_global_option('DFT_OMEGA', omega_l)
# Neutral
psi4.IO.change_file_namespace(180, "neutral", "ot")
molecule.set_molecular_charge(charge0)
molecule.set_multiplicity(mult0)
psi4.print_out("""\n\t==> IP Fitting SCF: Neutral, Left Endpoint <==\n""")
E0l, wfn = energy('scf', return_wfn=True, molecule=molecule, **kwargs)
eps_a = wfn.epsilon_a()
eps_b = wfn.epsilon_b()
E_HOMO = 0.0
if Nb == 0:
E_HOMO = eps_a[int(Na - 1)]
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if E_a >= E_b:
E_HOMO = E_a
else:
E_HOMO = E_b
E_HOMOl = E_HOMO
psi4.IO.change_file_namespace(180, "ot", "neutral")
# Cation
psi4.IO.change_file_namespace(180, "cation", "ot")
molecule.set_molecular_charge(charge1)
molecule.set_multiplicity(mult1)
psi4.print_out("""\n\t==> IP Fitting SCF: Cation, Left Endpoint <==\n""")
E1l = energy('scf', molecule=molecule, **kwargs)
psi4.IO.change_file_namespace(180, "ot", "cation")
IPl = E1l - E0l
kIPl = -E_HOMOl
delta_l = IPl - kIPl
if IPl < kIPl:
message = (
"""\n***IP Fitting Error: Left Omega limit should have kIP < IP""")
raise ValidationError(message)
omegas.append(omega_l)
types.append('Left Limit')
E0s.append(E0l)
E1s.append(E1l)
IPs.append(IPl)
kIPs.append(kIPl)
converged = False
repeat_l = 0
repeat_r = 0
step = 0
while True:
step = step + 1
# Regula Falsi (modified)
if repeat_l > 1:
delta_l = delta_l / 2.0
if repeat_r > 1:
delta_r = delta_r / 2.0
omega = -(omega_r - omega_l) / (delta_r - delta_l) * delta_l + omega_l
psi4.set_global_option('DFT_OMEGA', omega)
# Neutral
psi4.IO.change_file_namespace(180, "neutral", "ot")
molecule.set_molecular_charge(charge0)
molecule.set_multiplicity(mult0)
psi4.print_out(
"""\n\t==> IP Fitting SCF: Neutral, Omega = %11.3E <==\n""" %
omega)
E0, wfn = energy('scf', return_wfn=True, molecule=molecule, **kwargs)
eps_a = wfn.epsilon_a()
eps_b = wfn.epsilon_b()
E_HOMO = 0.0
if Nb == 0:
E_HOMO = eps_a[int(Na - 1)]
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if E_a >= E_b:
E_HOMO = E_a
else:
E_HOMO = E_b
psi4.IO.change_file_namespace(180, "ot", "neutral")
# Cation
psi4.IO.change_file_namespace(180, "cation", "ot")
molecule.set_molecular_charge(charge1)
molecule.set_multiplicity(mult1)
psi4.print_out(
"""\n\t==> IP Fitting SCF: Cation, Omega = %11.3E <==\n""" % omega)
E1 = energy('scf', molecule=molecule, **kwargs)
psi4.IO.change_file_namespace(180, "ot", "cation")
IP = E1 - E0
kIP = -E_HOMO
delta = IP - kIP
if kIP > IP:
omega_r = omega
E0r = E0
E1r = E1
IPr = IP
kIPr = kIP
delta_r = delta
repeat_r = 0
repeat_l = repeat_l + 1
else:
omega_l = omega
E0l = E0
E1l = E1
IPl = IP
kIPl = kIP
delta_l = delta
repeat_l = 0
repeat_r = repeat_r + 1
omegas.append(omega)
types.append('Regula-Falsi')
E0s.append(E0)
E1s.append(E1)
IPs.append(IP)
kIPs.append(kIP)
# Termination
if (abs(omega_l - omega_r) < omega_tol or step > maxiter):
converged = True
break
# Properly, should clone molecule but since not returned and easy to unblemish,
molecule.set_molecular_charge(charge0)
molecule.set_multiplicity(mult0)
psi4.IO.set_default_namespace("")
psi4.print_out("""\n\t==> IP Fitting Results <==\n\n""")
psi4.print_out("""\t => Occupation Determination <= \n\n""")
psi4.print_out("""\t %6s %6s %6s %6s %6s %6s\n""" %
('N', 'Na', 'Nb', 'Charge', 'Mult', 'H**O'))
psi4.print_out("""\t Neutral: %6d %6d %6d %6d %6d %6d\n""" %
(N, Na, Nb, charge0, mult0, H**O))
psi4.print_out("""\t Cation: %6d %6d %6d %6d %6d\n\n""" %
(N - 1, Na1, Nb1, charge1, mult1))
psi4.print_out("""\t => Regula Falsi Iterations <=\n\n""")
psi4.print_out("""\t%3s %11s %14s %14s %14s %s\n""" %
('N', 'Omega', 'IP', 'kIP', 'Delta', 'Type'))
for k in range(len(omegas)):
psi4.print_out(
"""\t%3d %11.3E %14.6E %14.6E %14.6E %s\n""" %
(k + 1, omegas[k], IPs[k], kIPs[k], IPs[k] - kIPs[k], types[k]))
if converged:
psi4.print_out("""\n\tIP Fitting Converged\n""")
psi4.print_out("""\tFinal omega = %14.6E\n""" %
((omega_l + omega_r) / 2))
psi4.print_out(
"""\n\t"M,I. does the dying. Fleet just does the flying."\n""")
psi4.print_out("""\t\t\t-Starship Troopers\n""")
else:
psi4.print_out("""\n\tIP Fitting did not converge!\n""")
psi4.set_global_option("DF_INTS_IO", "NONE")
psi4.set_global_option("GUESS", old_guess)
def __init__(self, msg):
PsiException.__init__(self, msg)
self.msg = msg
psi4.print_out('\nPsiException: %s\n\n' % (msg))
def ip_fitting(mol, omega_l, omega_r, **kwargs):
kwargs = p4util.kwargs_lower(kwargs)
# By default, zero the omega to 3 digits
omega_tol = 1.0E-3;
if (kwargs.has_key('omega_tolerance')):
omega_tol = kwargs['omega_tolerance']
# By default, do up to twenty iterations
maxiter = 20;
if (kwargs.has_key('maxiter')):
maxiter = kwargs['maxiter']
# By default, do not read previous 180 orbitals file
read = False;
read180 = ''
if (kwargs.has_key('read')):
read = True;
read180 = kwargs['read']
# The molecule is required, and should be the neutral species
mol.update_geometry()
activate(mol)
charge0 = mol.molecular_charge()
mult0 = mol.multiplicity()
# How many electrons are there?
N = 0;
for A in range(mol.natom()):
N += mol.Z(A)
N -= charge0
N = int(N)
Nb = int((N - mult0 + 1)/2)
Na = int(N - Nb)
# Work in the ot namespace for this procedure
psi4.IO.set_default_namespace("ot")
# Burn in to determine orbital eigenvalues
if (read):
psi4.set_global_option("GUESS", "READ")
copy_file_to_scratch(read180, 'psi', 'ot', 180)
old_guess = psi4.get_global_option("GUESS")
psi4.set_global_option("DF_INTS_IO", "SAVE")
psi4.print_out('\n\t==> IP Fitting SCF: Burn-in <==\n')
energy('scf')
psi4.set_global_option("DF_INTS_IO", "LOAD")
# Determine H**O, to determine mult1
ref = psi4.wavefunction()
eps_a = ref.epsilon_a()
eps_b = ref.epsilon_b()
if (Na == Nb):
H**O = -Nb
elif (Nb == 0):
H**O = Na
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if (E_a >= E_b):
H**O = Na
else:
H**O = -Nb
Na1 = Na;
Nb1 = Nb;
if (H**O > 0):
Na1 = Na1-1;
else:
Nb1 = Nb1-1;
charge1 = charge0 + 1;
mult1 = Na1 - Nb1 + 1
omegas = [];
E0s = [];
E1s = [];
kIPs = [];
IPs = [];
types = [];
# Right endpoint
psi4.set_global_option('DFT_OMEGA',omega_r)
# Neutral
if (read):
psi4.set_global_option("GUESS", "READ")
p4util.copy_file_to_scratch(read180, 'psi', 'ot', 180)
mol.set_molecular_charge(charge0)
mol.set_multiplicity(mult0)
psi4.print_out('\n\t==> IP Fitting SCF: Neutral, Right Endpoint <==\n')
E0r = energy('scf')
ref = psi4.wavefunction()
eps_a = ref.epsilon_a()
eps_b = ref.epsilon_b()
E_HOMO = 0.0;
if (Nb == 0):
E_HOMO = eps_a[int(Na-1)]
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if (E_a >= E_b):
E_HOMO = E_a;
else:
E_HOMO = E_b;
E_HOMOr = E_HOMO;
psi4.IO.change_file_namespace(180,"ot","neutral")
# Cation
if (read):
psi4.set_global_option("GUESS", "READ")
p4util.copy_file_to_scratch(read180, 'psi', 'ot', 180)
mol.set_molecular_charge(charge1)
mol.set_multiplicity(mult1)
psi4.print_out('\n\t==> IP Fitting SCF: Cation, Right Endpoint <==\n')
E1r = energy('scf')
psi4.IO.change_file_namespace(180,"ot","cation")
IPr = E1r - E0r;
kIPr = -E_HOMOr;
delta_r = IPr - kIPr;
if (IPr > kIPr):
psi4.print_out('\n***IP Fitting Error: Right Omega limit should have kIP > IP')
sys.exit(1)
omegas.append(omega_r)
types.append('Right Limit')
E0s.append(E0r)
E1s.append(E1r)
IPs.append(IPr)
kIPs.append(kIPr)
# Use previous orbitals from here out
psi4.set_global_option("GUESS","READ")
# Left endpoint
psi4.set_global_option('DFT_OMEGA',omega_l)
# Neutral
psi4.IO.change_file_namespace(180,"neutral","ot")
mol.set_molecular_charge(charge0)
mol.set_multiplicity(mult0)
psi4.print_out('\n\t==> IP Fitting SCF: Neutral, Left Endpoint <==\n')
E0l = energy('scf')
ref = psi4.wavefunction()
eps_a = ref.epsilon_a()
eps_b = ref.epsilon_b()
E_HOMO = 0.0;
if (Nb == 0):
E_HOMO = eps_a[int(Na-1)]
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if (E_a >= E_b):
E_HOMO = E_a;
else:
E_HOMO = E_b;
E_HOMOl = E_HOMO;
psi4.IO.change_file_namespace(180,"ot","neutral")
# Cation
psi4.IO.change_file_namespace(180,"cation","ot")
mol.set_molecular_charge(charge1)
mol.set_multiplicity(mult1)
psi4.print_out('\n\t==> IP Fitting SCF: Cation, Left Endpoint <==\n')
E1l = energy('scf')
psi4.IO.change_file_namespace(180,"ot","cation")
IPl = E1l - E0l;
kIPl = -E_HOMOl;
delta_l = IPl - kIPl;
if (IPl < kIPl):
psi4.print_out('\n***IP Fitting Error: Left Omega limit should have kIP < IP')
sys.exit(1)
omegas.append(omega_l)
types.append('Left Limit')
E0s.append(E0l)
E1s.append(E1l)
IPs.append(IPl)
kIPs.append(kIPl)
converged = False
repeat_l = 0;
repeat_r = 0;
step = 0;
while True:
step = step + 1;
# Regula Falsi (modified)
if (repeat_l > 1):
delta_l = delta_l / 2.0;
if (repeat_r > 1):
delta_r = delta_r / 2.0;
omega = - (omega_r - omega_l) / (delta_r - delta_l) * delta_l + omega_l;
psi4.set_global_option('DFT_OMEGA',omega)
# Neutral
psi4.IO.change_file_namespace(180,"neutral","ot")
mol.set_molecular_charge(charge0)
mol.set_multiplicity(mult0)
psi4.print_out('\n\t==> IP Fitting SCF: Neutral, Omega = %11.3E <==\n' % omega)
E0 = energy('scf')
ref = psi4.wavefunction()
eps_a = ref.epsilon_a()
eps_b = ref.epsilon_b()
E_HOMO = 0.0;
if (Nb == 0):
E_HOMO = eps_a[int(Na-1)]
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if (E_a >= E_b):
E_HOMO = E_a;
else:
E_HOMO = E_b;
psi4.IO.change_file_namespace(180,"ot","neutral")
# Cation
psi4.IO.change_file_namespace(180,"cation","ot")
mol.set_molecular_charge(charge1)
mol.set_multiplicity(mult1)
psi4.print_out('\n\t==> IP Fitting SCF: Cation, Omega = %11.3E <==\n' % omega)
E1 = energy('scf')
psi4.IO.change_file_namespace(180,"ot","cation")
IP = E1 - E0;
kIP = -E_HOMO;
delta = IP - kIP;
if (kIP > IP):
omega_r = omega
E0r = E0
E1r = E1
IPr = IP
kIPr = kIP
delta_r = delta
repeat_r = 0;
repeat_l = repeat_l + 1;
else:
omega_l = omega
E0l = E0
E1l = E1
IPl = IP
kIPl = kIP
delta_l = delta
repeat_l = 0;
repeat_r = repeat_r + 1;
omegas.append(omega)
types.append('Regula-Falsi')
E0s.append(E0)
E1s.append(E1)
IPs.append(IP)
kIPs.append(kIP)
# Termination
if (abs(omega_l - omega_r) < omega_tol or step > maxiter):
converged = True;
break
psi4.IO.set_default_namespace("")
psi4.print_out('\n\t==> IP Fitting Results <==\n\n')
psi4.print_out('\t => Occupation Determination <= \n\n')
psi4.print_out('\t %6s %6s %6s %6s %6s %6s\n' %('N', 'Na', 'Nb', 'Charge', 'Mult', 'H**O'))
psi4.print_out('\t Neutral: %6d %6d %6d %6d %6d %6d\n' %(N, Na, Nb, charge0, mult0, H**O))
psi4.print_out('\t Cation: %6d %6d %6d %6d %6d\n\n' %(N-1, Na1, Nb1, charge1, mult1))
psi4.print_out('\t => Regula Falsi Iterations <=\n\n')
psi4.print_out('\t%3s %11s %14s %14s %14s %s\n' % ('N','Omega','IP','kIP','Delta','Type'))
for k in range(len(omegas)):
psi4.print_out('\t%3d %11.3E %14.6E %14.6E %14.6E %s\n' % (k+1,omegas[k],IPs[k],kIPs[k],IPs[k] - kIPs[k], types[k]))
if (converged):
psi4.print_out('\n\tIP Fitting Converged\n')
psi4.print_out('\tFinal omega = %14.6E\n' % ((omega_l + omega_r) / 2))
psi4.print_out('\n\t"M,I. does the dying. Fleet just does the flying."\n')
psi4.print_out('\t\t\t-Starship Troopers\n')
else:
psi4.print_out('\n\tIP Fitting did not converge!\n')
psi4.set_global_option("DF_INTS_IO", "NONE")
psi4.set_global_option("GUESS", old_guess)
def __init__(self, msg):
PsiException.__init__(self, msg)
self.msg = msg
psi4.print_out('\nPsiException: %s\n\n' % (msg))
def ccsd_energy(self):
indx, Ep1, Ep2, g = self.indx, self.Ep1, self.Ep2, self.g
t1 = indx.zeros('ia')
t2 = indx.einsum('ijab', (g, "ijab"), (Ep2, "ijab"))
for i in range(maxiter):
t1 = Ep1 * indx.meinsums(
'ia', # Crawford p. 59
[1., I, (g, "kaci"), (t1, "kc")],
[1. / 2, I, (g, "kacd"), (t2, "kicd")],
[-1. / 2, I, (g, "klci"), (t2, "klca")],
[-1., I, (g, "klci"), (t1, "kc"), (t1, "la")],
[1., I, (g, "kacd"), (t1, "kc"), (t1, "id")],
[-1., I, (g, "klcd"), (t1, "kc"), (t1, "id"), (t1, "la")],
[1., I, (g, "klcd"), (t1, "kc"), (t2, "lida")],
[-1. / 2, I, (g, "klcd"), (t2, "kicd"), (t1, "la")],
[-1. / 2, I, (g, "klcd"), (t2, "klca"), (t1, "id")])
t2 = Ep2 * indx.meinsums(
'ijab', # Crawford, p. 59-60
[1., I, (g, "abij")],
[1. / 2, I, (g, "klij"), (t2, "klab")],
[1. / 2, I, (g, "abcd"), (t2, "ijcd")],
[1., P("ij|ab"), (g, "kbcj"), (t2, "ikac")],
[1., P("ij"), (g, "abcj"), (t1, "ic")],
[-1., P("ab"), (g, "kbij"), (t1, "ka")],
[1. / 2,
P("ij|ab"), (g, "klcd"), (t2, "ikac"), (t2, "ljdb")],
[1. / 4, I, (g, "klcd"), (t2, "ijcd"), (t2, "klab")],
[-1. / 2,
P("ab"), (g, "klcd"), (t2, "ijac"), (t2, "klbd")],
[-1. / 2,
P("ij"), (g, "klcd"), (t2, "ikab"), (t2, "jlcd")],
[1. / 2, P("ab"), (g, "klij"), (t1, "ka"), (t1, "lb")],
[1. / 2, P("ij"), (g, "abcd"), (t1, "ic"), (t1, "jd")],
[-1., P("ij|ab"), (g, "kbic"), (t1, "ka"), (t1, "jc")],
[-1., P("ij"), (g, "klci"), (t1, "kc"), (t2, "ljab")],
[1., P("ab"), (g, "kacd"), (t1, "kc"), (t2, "ijdb")],
[1., P("ij|ab"), (g, "akdc"), (t1, "id"), (t2, "jkbc")],
[1., P("ij|ab"), (g, "klic"), (t1, "la"), (t2, "jkbc")],
[1. / 2,
P("ij"), (g, "klcj"), (t1, "ic"), (t2, "klab")],
[-1. / 2,
P("ab"), (g, "kbcd"), (t1, "ka"), (t2, "ijcd")],
[
-1. / 2,
P("ij|ab"), (g, "kbcd"), (t1, "ic"), (t1, "ka"), (t1, "jd")
],
[
1. / 2,
P("ij|ab"), (g, "klcj"), (t1, "ic"), (t1, "ka"), (t1, "lb")
],
[
-1.,
P("ij"), (g, "klcd"), (t1, "kc"), (t1, "id"), (t2, "ljab")
],
[
-1.,
P("ab"), (g, "klcd"), (t1, "kc"), (t1, "la"), (t2, "ijdb")
],
[
1. / 4,
P("ij"), (g, "klcd"), (t1, "ic"), (t1, "jd"), (t2, "klab")
],
[
1. / 4,
P("ab"), (g, "klcd"), (t1, "ka"), (t1, "lb"), (t2, "ijcd")
],
[
1.,
P("ij|ab"), (g, "klcd"), (t1, "ic"), (t1, "lb"),
(t2, "kjad")
],
[
1. / 4,
P("ij|ab"), (g, "klcd"), (t1, "ic"), (t1, "ka"),
(t1, "jd"), (t1, "lb")
])
E = indx.meinsums('', [1. / 4, I, (g, "ijab"), (t2, "ijab")],
[1. / 2, I, (g, "ijab"), (t1, "ia"), (t1, "jb")])
dE = E - self.E
self.E = E
psi4.print_out('\n@CCSD{:-3d}{:20.15f}{:20.15f}'.format(i, E, dE))
if (abs(dE) < econv): break
return self.E
def anharmonicity(rvals, energies, mol=None):
"""Generates spectroscopic constants for a diatomic molecules.
Fits a diatomic potential energy curve using either a 5 or 9 point Legendre fit, locates the minimum
energy point, and then applies second order vibrational perturbation theory to obtain spectroscopic
constants. The r values provided must bracket the minimum energy point, or an error will result.
A dictionary with the following keys, which correspond to spectroscopic constants, is returned:
:type rvals: list
:param rvals: The bond lengths (in Angstrom) for which energies are
provided of length either 5 or 9 but must be the same length as
the energies array
:type energies: list
:param energies: The energies (Eh) computed at the bond lengths in the rvals list
:returns: (*dict*) Keys: "re", "r0", "we", "wexe", "nu", "ZPVE(harmonic)", "ZPVE(anharmonic)", "Be", "B0", "ae", "De"
corresponding to the spectroscopic constants in cm-1
"""
angstrom_to_bohr = 1.0 / p4const.psi_bohr2angstroms
angstrom_to_meter = 10e-10
if len(rvals) != len(energies):
raise Exception(
"The number of energies must match the number of distances")
npoints = len(rvals)
if npoints != 5 and npoints != 9:
raise Exception("Only 5- or 9-point fits are implemented right now")
psi4.print_out("\n\nPerforming a %d-point fit\n" % npoints)
psi4.print_out("\nOptimizing geometry based on current surface:\n\n")
if (npoints == 5):
optx = rvals[2]
elif (npoints == 9):
optx = rvals[4]
# Molecule can be passed in be user. Look at the function definition above.
if mol == None:
mol = psi4.get_active_molecule()
natoms = mol.natom()
if natoms != 2:
raise Exception(
"The current molecule must be a diatomic for this code to work!")
m1 = mol.mass(0)
m2 = mol.mass(1)
maxit = 30
thres = 1.0e-9
for i in range(maxit):
if (npoints == 5):
grad = first_deriv_5pt(rvals, energies, optx)
secd = second_deriv_5pt(rvals, energies, optx)
energy = function_5pt(rvals, energies, optx)
elif (npoints == 9):
grad = first_deriv_9pt(rvals, energies, optx)
secd = second_deriv_9pt(rvals, energies, optx)
energy = function_9pt(rvals, energies, optx)
psi4.print_out(" E = %20.14f, x = %14.7f, grad = %20.14f\n" %
(energy, optx, grad))
if abs(grad) < thres:
break
optx -= grad / secd
psi4.print_out(" Final E = %20.14f, x = %14.7f, grad = %20.14f\n" %
(function_5pt(rvals, energies, optx), optx, grad))
if optx < min(rvals):
raise Exception(
"Minimum energy point is outside range of points provided. Use a lower range of r values."
)
if optx > max(rvals):
raise Exception(
"Minimum energy point is outside range of points provided. Use a higher range of r values."
)
if (npoints == 5):
energy = function_5pt(rvals, energies, optx)
first = first_deriv_5pt(rvals, energies, optx)
secd = second_deriv_5pt(rvals, energies, optx) * p4const.psi_hartree2aJ
third = third_deriv_5pt(rvals, energies, optx) * p4const.psi_hartree2aJ
fourth = fourth_deriv_5pt(rvals, energies,
optx) * p4const.psi_hartree2aJ
elif (npoints == 9):
energy = function_9pt(rvals, energies, optx)
first = first_deriv_9pt(rvals, energies, optx)
secd = second_deriv_9pt(rvals, energies, optx) * p4const.psi_hartree2aJ
third = third_deriv_9pt(rvals, energies, optx) * p4const.psi_hartree2aJ
fourth = fourth_deriv_9pt(rvals, energies,
optx) * p4const.psi_hartree2aJ
psi4.print_out("\nEquilibrium Energy %20.14f Hartrees\n" % energy)
psi4.print_out("Gradient %20.14f\n" % first)
psi4.print_out("Quadratic Force Constant %14.7f MDYNE/A\n" % secd)
psi4.print_out("Cubic Force Constant %14.7f MDYNE/A**2\n" % third)
psi4.print_out("Quartic Force Constant %14.7f MDYNE/A**3\n" % fourth)
hbar = p4const.psi_h / (2.0 * pi)
mu = ((m1 * m2) / (m1 + m2)) * p4const.psi_amu2kg
we = 5.3088375e-11 * sqrt(secd / mu)
wexe = (1.2415491e-6) * (we / secd)**2 * ((5.0 * third * third) /
(3.0 * secd) - fourth)
# Rotational constant: Be
I = ((m1 * m2) /
(m1 + m2)) * p4const.psi_amu2kg * (optx * angstrom_to_meter)**2
B = p4const.psi_h / (8.0 * pi**2 * p4const.psi_c * I)
# alpha_e and quartic centrifugal distortion constant
ae = -(6.0 * B**2 / we) * ((1.05052209e-3 * we * third) /
(sqrt(B * secd**3)) + 1.0)
de = 4.0 * B**3 / we**2
# B0 and r0 (plus re check using Be)
B0 = B - ae / 2.0
r0 = sqrt(p4const.psi_h / (8.0 * pi**2 * mu * p4const.psi_c * B0))
recheck = sqrt(p4const.psi_h / (8.0 * pi**2 * mu * p4const.psi_c * B))
r0 /= angstrom_to_meter
recheck /= angstrom_to_meter
# Fundamental frequency nu
nu = we - 2.0 * wexe
zpve_nu = 0.5 * we - 0.25 * wexe
psi4.print_out("\nre = %10.6f A check: %10.6f\n" % (optx, recheck))
psi4.print_out("r0 = %10.6f A\n" % r0)
psi4.print_out("we = %10.4f cm-1\n" % we)
psi4.print_out("wexe = %10.4f cm-1\n" % wexe)
psi4.print_out("nu = %10.4f cm-1\n" % nu)
psi4.print_out("ZPVE(nu) = %10.4f cm-1\n" % zpve_nu)
psi4.print_out("Be = %10.4f cm-1\n" % B)
psi4.print_out("B0 = %10.4f cm-1\n" % B0)
psi4.print_out("ae = %10.4f cm-1\n" % ae)
psi4.print_out("De = %10.7f cm-1\n" % de)
results = {
"re": optx,
"r0": r0,
"we": we,
"wexe": wexe,
"nu": nu,
"ZPVE(harmonic)": zpve_nu,
"ZPVE(anharmonic)": zpve_nu,
"Be": B,
"B0": B0,
"ae": ae,
"De": de
}
return results
def run_roa(name, **kwargs):
"""
Main driver for managing Raman Optical activity computations with
CC response theory.
Uses distributed finite differences approach -->
1. Sets up a database to keep track of running/finished/waiting
computations.
2. Generates separate input files for displaced geometries.
3. When all displacements are run, collects the necessary information
from each displaced computation, and computes final result.
"""
# Get list of omega values -> Make sure we only have one wavelength
# Catch this now before any real work gets done
omega = psi4.get_option('CCRESPONSE', 'OMEGA')
if len(omega) > 2:
raise Exception(
'ROA scattering can only be performed for one wavelength.')
else:
pass
psi4.print_out('Running ROA computation. Subdirectories for each '
'required displaced geometry have been created.\n\n')
dbno = 0
# Initialize database
db = shelve.open('database', writeback=True)
# Check if final result is in here
# ->if we have already computed roa, back up the dict
# ->copy it setting this flag to false and continue
if ('roa_computed' in db) and (db['roa_computed']):
db2 = shelve.open('.database.bak{}'.format(dbno), writeback=True)
dbno += 1
for key, value in db.iteritems():
db2[key] = value
db2.close()
db['roa_computed'] = False
else:
db['roa_computed'] = False
if 'inputs_generated' not in db:
findif_response_utils.initialize_database(db, name, "roa",
["roa_tensor"])
# Generate input files
if not db['inputs_generated']:
findif_response_utils.generate_inputs(db, name)
# handled by helper db['inputs_generated'] = True
# Check job status
if db['inputs_generated'] and not db['jobs_complete']:
print('Checking status')
findif_response_utils.stat(db)
for job, status in db['job_status'].items():
print("{} --> {}".format(job, status))
# Compute ROA Scattering
if db['jobs_complete']:
mygauge = psi4.get_option('CCRESPONSE', 'GAUGE')
consider_gauge = {
'LENGTH': ['Length Gauge'],
'VELOCITY': ['Modified Velocity Gauge'],
'BOTH': ['Length Gauge', 'Modified Velocity Gauge']
}
gauge_list = ["{} Results".format(x) for x in consider_gauge[mygauge]]
# Gather data
dip_polar_list = findif_response_utils.collect_displaced_matrix_data(
db, 'Dipole Polarizability', 3)
opt_rot_list = [
x for x in (findif_response_utils.collect_displaced_matrix_data(
db, "Optical Rotation Tensor ({})".format(gauge), 3)
for gauge in consider_gauge[mygauge])
]
dip_quad_polar_list = findif_response_utils.collect_displaced_matrix_data(
db, "Electric-Dipole/Quadrupole Polarizability", 9)
# Compute Scattering
# Run new function (src/bin/ccresponse/scatter.cc)
psi4.print_out('Running scatter function')
step = psi4.get_local_option('FINDIF', 'DISP_SIZE')
for g_idx, gauge in enumerate(opt_rot_list):
print(
'\n\n----------------------------------------------------------------------'
)
print('\t%%%%%%%%%% {} %%%%%%%%%%'.format(gauge_list[g_idx]))
print(
'----------------------------------------------------------------------\n\n'
)
psi4.print_out(
'\n\n----------------------------------------------------------------------\n'
)
psi4.print_out('\t%%%%%%%%%% {} %%%%%%%%%%\n'.format(
gauge_list[g_idx]))
psi4.print_out(
'----------------------------------------------------------------------\n\n'
)
print(
'roa.py:85 I am not being passed a molecule, grabbing from global :('
)
psi4.scatter(psi4.get_active_molecule(), step, dip_polar_list,
gauge, dip_quad_polar_list)
db['roa_computed'] = True
db.close()
def frac_traverse(molecule, **kwargs):
kwargs = p4util.kwargs_lower(kwargs)
# The molecule is required, and should be the neutral species
molecule.update_geometry()
charge0 = molecule.molecular_charge()
mult0 = molecule.multiplicity()
chargep = charge0 + 1
chargem = charge0 - 1
# By default, the multiplicity of the cation/anion are mult0 + 1
# These are overridden with the cation_mult and anion_mult kwargs
multp = kwargs.get('cation_mult', mult0 + 1)
multm = kwargs.get('anion_mult', mult0 + 1)
# By default, we start the frac procedure on the 25th iteration
# when not reading a previous guess
frac_start = kwargs.get('frac_start', 25)
# By default, we occupy by tenths of electrons
HOMO_occs = kwargs.get(
'HOMO_occs', [1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.0])
LUMO_occs = kwargs.get(
'LUMO_occs', [1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.0])
# By default, H**O and LUMO are both in alpha
Z = 0
for A in range(molecule.natom()):
Z += molecule.Z(A)
Z -= charge0
H**O = kwargs.get('H**O', (Z / 2 + 1 if (Z % 2) else Z / 2))
LUMO = kwargs.get('LUMO', H**O + 1)
# By default, DIIS in FRAC (1.0 occupation is always DIIS'd)
frac_diis = kwargs.get('frac_diis', True)
# By default, use the neutral orbitals as a guess for the anion
neutral_guess = kwargs.get('neutral_guess', True)
# By default, burn-in with UHF first, if UKS
hf_guess = False
if psi4.get_global_option('REFERENCE') == 'UKS':
hf_guess = kwargs.get('hf_guess', True)
# By default, re-guess at each N
continuous_guess = kwargs.get('continuous_guess', False)
# By default, drop the files to the molecule's name
root = kwargs.get('filename', molecule.name())
traverse_filename = root + '.traverse.dat'
# => Traverse <= #
occs = []
energies = []
potentials = []
convs = []
# => Run the neutral for its orbitals, if requested <= #
old_df_ints_io = psi4.get_global_option("DF_INTS_IO")
psi4.set_global_option("DF_INTS_IO", "SAVE")
old_guess = psi4.get_global_option("GUESS")
if (neutral_guess):
if (hf_guess):
psi4.set_global_option("REFERENCE", "UHF")
energy('scf')
psi4.set_global_option("GUESS", "READ")
psi4.set_global_option("DF_INTS_IO", "LOAD")
# => Run the anion first <= #
molecule.set_molecular_charge(chargem)
molecule.set_multiplicity(multm)
# => Burn the anion in with hf, if requested <= #
if hf_guess:
psi4.set_global_option("REFERENCE", "UHF")
energy('scf', molecule=molecule, **kwargs)
psi4.set_global_option("REFERENCE", "UKS")
psi4.set_global_option("GUESS", "READ")
psi4.set_global_option("DF_INTS_IO", "SAVE")
psi4.set_global_option("FRAC_START", frac_start)
psi4.set_global_option("FRAC_RENORMALIZE", True)
psi4.set_global_option("FRAC_LOAD", False)
for occ in LUMO_occs:
psi4.set_global_option("FRAC_OCC", [LUMO])
psi4.set_global_option("FRAC_VAL", [occ])
E, wfn = energy('scf', return_wfn=True, molecule=molecule, **kwargs)
C = 1
if E == 0.0:
E = psi4.get_variable('SCF ITERATION ENERGY')
C = 0
if LUMO > 0:
eps = wfn.epsilon_a()
potentials.append(eps[int(LUMO) - 1])
else:
eps = wfn.epsilon_b()
potentials.append(eps[-int(LUMO) - 1])
occs.append(occ)
energies.append(E)
convs.append(C)
psi4.set_global_option("FRAC_START", 2)
psi4.set_global_option("FRAC_LOAD", True)
psi4.set_global_option("GUESS", "READ")
psi4.set_global_option("FRAC_DIIS", frac_diis)
psi4.set_global_option("DF_INTS_IO", "LOAD")
# => Run the neutral next <= #
molecule.set_molecular_charge(charge0)
molecule.set_multiplicity(mult0)
# Burn the neutral in with hf, if requested <= #
if not continuous_guess:
psi4.set_global_option("GUESS", old_guess)
if hf_guess:
psi4.set_global_option("FRAC_START", 0)
psi4.set_global_option("REFERENCE", "UHF")
energy('scf', molecule=molecule, **kwargs)
psi4.set_global_option("REFERENCE", "UKS")
psi4.set_global_option("GUESS", "READ")
psi4.set_global_option("FRAC_LOAD", False)
psi4.set_global_option("FRAC_START", frac_start)
psi4.set_global_option("FRAC_RENORMALIZE", True)
for occ in HOMO_occs:
psi4.set_global_option("FRAC_OCC", [H**O])
psi4.set_global_option("FRAC_VAL", [occ])
E, wfn = energy('scf', return_wfn=True, molecule=molecule, **kwargs)
C = 1
if E == 0.0:
E = psi4.get_variable('SCF ITERATION ENERGY')
C = 0
if LUMO > 0:
eps = wfn.epsilon_a()
potentials.append(eps[int(H**O) - 1])
else:
eps = wfn.epsilon_b()
potentials.append(eps[-int(H**O) - 1])
occs.append(occ - 1.0)
energies.append(E)
convs.append(C)
psi4.set_global_option("FRAC_START", 2)
psi4.set_global_option("FRAC_LOAD", True)
psi4.set_global_option("GUESS", "READ")
psi4.set_global_option("FRAC_DIIS", frac_diis)
psi4.set_global_option("DF_INTS_IO", "LOAD")
psi4.set_global_option("DF_INTS_IO", old_df_ints_io)
# => Print the results out <= #
E = {}
psi4.print_out(
"""\n ==> Fractional Occupation Traverse Results <==\n\n""")
psi4.print_out("""\t%-11s %-24s %-24s %11s\n""" %
('N', 'Energy', 'H**O Energy', 'Converged'))
for k in range(len(occs)):
psi4.print_out("""\t%11.3E %24.16E %24.16E %11d\n""" %
(occs[k], energies[k], potentials[k], convs[k]))
E[occs[k]] = energies[k]
psi4.print_out('\n\t"You trying to be a hero Watkins?"\n')
psi4.print_out('\t"Just trying to kill some bugs sir!"\n')
psi4.print_out('\t\t\t-Starship Troopers\n')
# Drop the files out
fh = open(traverse_filename, 'w')
fh.write("""\t%-11s %-24s %-24s %11s\n""" %
('N', 'Energy', 'H**O Energy', 'Converged'))
for k in range(len(occs)):
fh.write("""\t%11.3E %24.16E %24.16E %11d\n""" %
(occs[k], energies[k], potentials[k], convs[k]))
fh.close()
# Properly, should clone molecule but since not returned and easy to unblemish,
molecule.set_molecular_charge(charge0)
molecule.set_multiplicity(mult0)
return E
def run_roa(name, **kwargs):
# Get list of omega values -> Make sure we only have one wavelength
# Catch this now before any real work gets done
omega = psi4.get_option('CCRESPONSE', 'OMEGA')
if len(omega) > 2:
raise Exception(
'ROA scattering can only be performed for one wavelength.')
else:
pass
psi4.print_out('Running ROA computation. Subdirectories for each '
'required displaced geometry have been created.\n\n')
### Initialize database
db = shelve.open('database', writeback=True)
if 'inputs_generated' not in db:
initialize_database(db)
### Generate input files
if not db['inputs_generated']:
generate_inputs(name, db)
db['inputs_generated'] = True
### If 'serial' calculation, proceed with subdir execution
### Check job status
if db['inputs_generated'] and not db['jobs_complete']:
print('Checking status')
roa_stat(db)
for job, status in db['job_status'].items():
print("{} --> {}".format(job, status))
### Compute ROA Scattering
if db['jobs_complete']:
# SAVE this for when multiple wavelengths works
# # Get list of omega values
# omega = psi4.get_option('CCRESPONSE','OMEGA')
# if len(omega) > 1:
# units = copy.copy(omega[-1])
# omega.pop()
# else:
# units = 'atomic'
# wavelength = copy.copy(omega[0])
# # Set up units for scatter.cc
# if units == 'NM':
# wavelength = (psi_c * psi_h * 1*(10**-9))/(wavelength * psi_hartree2J)
# if units == 'HZ':
# wavelength = wavelength * psi_h / psi_hartree2J
# if units == 'EV':
# wavelength = wavelength / psi_hartree2ev
# if units == 'atomic':
# pass
# Initialize tensor lists
dip_polar_list = []
opt_rot_list = []
dip_quad_polar_list = []
gauge_list = []
make_gauge_list(gauge_list)
# Gather data
synthesize_dipole_polar(db, dip_polar_list)
synthesize_opt_rot(db, opt_rot_list)
synthesize_dip_quad_polar(db, dip_quad_polar_list)
# Compute Scattering
# Run new function (src/bin/ccresponse/scatter.cc)
psi4.print_out('Running scatter function')
step = psi4.get_local_option('FINDIF', 'DISP_SIZE')
for gauge in opt_rot_list:
g_idx = opt_rot_list.index(gauge)
# print('\n\n----------------------------------------------------------------------')
# print('\t%%%%%%%%%% {} %%%%%%%%%%'.format(gauge_list[g_idx]))
# print('----------------------------------------------------------------------\n\n')
psi4.print_out(
'\n\n----------------------------------------------------------------------\n'
)
psi4.print_out('\t%%%%%%%%%% {} %%%%%%%%%%\n'.format(
gauge_list[g_idx]))
psi4.print_out(
'----------------------------------------------------------------------\n\n'
)
psi4.scatter(step, dip_polar_list, gauge, dip_quad_polar_list)
db.close()
def anharmonicity(rvals, energies, mol = None):
"""Generates spectroscopic constants for a diatomic molecules.
Fits a diatomic potential energy curve using either a 5 or 9 point Legendre fit, locates the minimum
energy point, and then applies second order vibrational perturbation theory to obtain spectroscopic
constants. The r values provided must bracket the minimum energy point, or an error will result.
A dictionary with the following keys, which correspond to spectroscopic constants, is returned:
:type rvals: list
:param rvals: The bond lengths (in Angstrom) for which energies are
provided of length either 5 or 9 but must be the same length as
the energies array
:type energies: list
:param energies: The energies (Eh) computed at the bond lengths in the rvals list
:returns: (*dict*) Keys: "re", "r0", "we", "wexe", "nu", "ZPVE(harmonic)", "ZPVE(anharmonic)", "Be", "B0", "ae", "De"
corresponding to the spectroscopic constants in cm-1
"""
angstrom_to_bohr = 1.0 / p4const.psi_bohr2angstroms
angstrom_to_meter = 10e-10;
if len(rvals) != len(energies):
raise Exception("The number of energies must match the number of distances")
npoints = len(rvals)
if npoints != 5 and npoints != 9:
raise Exception("Only 5- or 9-point fits are implemented right now")
psi4.print_out("\n\nPerforming a %d-point fit\n" % npoints)
psi4.print_out("\nOptimizing geometry based on current surface:\n\n");
if (npoints == 5):
optx = rvals[2]
elif (npoints == 9):
optx = rvals[4]
# Molecule can be passed in be user. Look at the function definition above.
if mol == None:
mol = psi4.get_active_molecule()
natoms = mol.natom()
if natoms != 2:
raise Exception("The current molecule must be a diatomic for this code to work!")
m1 = mol.mass(0)
m2 = mol.mass(1)
maxit = 30
thres = 1.0e-9
for i in range(maxit):
if (npoints == 5):
grad= first_deriv_5pt(rvals, energies, optx)
secd = second_deriv_5pt(rvals, energies, optx)
energy = function_5pt(rvals, energies, optx)
elif (npoints == 9):
grad = first_deriv_9pt(rvals, energies, optx)
secd = second_deriv_9pt(rvals, energies, optx)
energy = function_9pt(rvals, energies, optx)
psi4.print_out(" E = %20.14f, x = %14.7f, grad = %20.14f\n" % (energy, optx, grad))
if abs(grad) < thres:
break
optx -= grad / secd;
psi4.print_out(" Final E = %20.14f, x = %14.7f, grad = %20.14f\n" % (function_5pt(rvals, energies, optx), optx, grad));
if optx < min(rvals):
raise Exception("Minimum energy point is outside range of points provided. Use a lower range of r values.")
if optx > max(rvals):
raise Exception("Minimum energy point is outside range of points provided. Use a higher range of r values.")
if (npoints == 5):
energy = function_5pt(rvals, energies, optx)
first = first_deriv_5pt(rvals, energies, optx)
secd = second_deriv_5pt(rvals, energies, optx) * p4const.psi_hartree2aJ
third = third_deriv_5pt(rvals, energies, optx) * p4const.psi_hartree2aJ
fourth = fourth_deriv_5pt(rvals, energies, optx) * p4const.psi_hartree2aJ
elif (npoints == 9):
energy = function_9pt(rvals, energies, optx)
first = first_deriv_9pt(rvals, energies, optx)
secd = second_deriv_9pt(rvals, energies, optx) * p4const.psi_hartree2aJ
third = third_deriv_9pt(rvals, energies, optx) * p4const.psi_hartree2aJ
fourth = fourth_deriv_9pt(rvals, energies, optx) * p4const.psi_hartree2aJ
psi4.print_out("\nEquilibrium Energy %20.14f Hartrees\n" % energy)
psi4.print_out("Gradient %20.14f\n" % first)
psi4.print_out("Quadratic Force Constant %14.7f MDYNE/A\n" % secd)
psi4.print_out("Cubic Force Constant %14.7f MDYNE/A**2\n" % third)
psi4.print_out("Quartic Force Constant %14.7f MDYNE/A**3\n" % fourth)
hbar = p4const.psi_h / (2.0 * pi)
mu = ((m1*m2)/(m1+m2))*p4const.psi_amu2kg
we = 5.3088375e-11*sqrt(secd/mu)
wexe = (1.2415491e-6)*(we/secd)**2 * ((5.0*third*third)/(3.0*secd)-fourth)
# Rotational constant: Be
I = ((m1*m2)/(m1+m2)) * p4const.psi_amu2kg * (optx * angstrom_to_meter)**2
B = p4const.psi_h / (8.0 * pi**2 * p4const.psi_c * I)
# alpha_e and quartic centrifugal distortion constant
ae = -(6.0 * B**2 / we) * ((1.05052209e-3*we*third)/(sqrt(B * secd**3))+1.0)
de = 4.0*B**3 / we**2
# B0 and r0 (plus re check using Be)
B0 = B - ae / 2.0
r0 = sqrt(p4const.psi_h / (8.0 * pi**2 * mu * p4const.psi_c * B0))
recheck = sqrt(p4const.psi_h / (8.0 * pi**2 * mu * p4const.psi_c * B))
r0 /= angstrom_to_meter;
recheck /= angstrom_to_meter;
# Fundamental frequency nu
nu = we - 2.0 * wexe;
zpve_nu = 0.5 * we - 0.25 * wexe;
psi4.print_out("\nre = %10.6f A check: %10.6f\n" % (optx, recheck))
psi4.print_out("r0 = %10.6f A\n" % r0)
psi4.print_out("we = %10.4f cm-1\n" % we)
psi4.print_out("wexe = %10.4f cm-1\n" % wexe)
psi4.print_out("nu = %10.4f cm-1\n" % nu)
psi4.print_out("ZPVE(nu) = %10.4f cm-1\n" % zpve_nu)
psi4.print_out("Be = %10.4f cm-1\n" % B)
psi4.print_out("B0 = %10.4f cm-1\n" % B0)
psi4.print_out("ae = %10.4f cm-1\n" % ae)
psi4.print_out("De = %10.7f cm-1\n" % de)
results = {
"re" : optx,
"r0" : r0,
"we" : we,
"wexe" : wexe,
"nu" : nu,
"ZPVE(harmonic)" : zpve_nu,
"ZPVE(anharmonic)" : zpve_nu,
"Be" : B,
"B0" : B0,
"ae" : ae,
"De" : de
}
return results
def auto_fragments(**kwargs):
r"""Detects fragments if the user does not supply them.
Currently only used for the WebMO implementation of SAPT.
:returns: :ref:`Molecule<sec:psimod_Molecule>`) |w--w| fragmented molecule.
:type molecule: :ref:`molecule <op_py_molecule>`
:param molecule: ``h2o`` || etc.
The target molecule, if not the last molecule defined.
:examples:
>>> # [1] replicates with cbs() the simple model chemistry scf/cc-pVDZ: set basis cc-pVDZ energy('scf')
>>> molecule mol {\nH 0.0 0.0 0.0\nH 2.0 0.0 0.0\nF 0.0 1.0 0.0\nF 2.0 1.0 0.0\n}
>>> print mol.nfragments() # 1
>>> fragmol = auto_fragments()
>>> print fragmol.nfragments() # 2
"""
# Make sure the molecule the user provided is the active one
molecule = kwargs.pop('molecule', psi4.get_active_molecule())
molecule.update_geometry()
molname = molecule.name()
geom = molecule.save_string_xyz()
numatoms = molecule.natom()
VdW = [1.2, 1.7, 1.5, 1.55, 1.52, 1.9, 1.85, 1.8]
symbol = list(range(numatoms))
X = [0.0] * numatoms
Y = [0.0] * numatoms
Z = [0.0] * numatoms
Queue = []
White = []
Black = []
F = geom.split('\n')
for f in range(numatoms):
A = F[f + 1].split()
symbol[f] = A[0]
X[f] = float(A[1])
Y[f] = float(A[2])
Z[f] = float(A[3])
White.append(f)
Fragment = [[] for i in range(numatoms)] # stores fragments
start = 0 # starts with the first atom in the list
Queue.append(start)
White.remove(start)
frag = 0
while ((len(White) > 0)
or (len(Queue) > 0)): # Iterates to the next fragment
while (len(Queue) > 0): # BFS within a fragment
for u in Queue: # find all nearest Neighbors
# (still coloured white) to vertex u
for i in White:
Distance = math.sqrt((X[i] - X[u]) * (X[i] - X[u]) +
(Y[i] - Y[u]) * (Y[i] - Y[u]) +
(Z[i] - Z[u]) * (Z[i] - Z[u]))
if Distance < _autofragment_convert(
u, symbol) + _autofragment_convert(i, symbol):
Queue.append(i) # if you find you, put it in the que
White.remove(
i) # and remove it from the untouched list
Queue.remove(u) # remove focus from Queue
Black.append(u)
Fragment[frag].append(int(u +
1)) # add to group (adding 1 to start
# list at one instead of zero)
if (len(White) != 0): # cant move White->Queue if no more exist
Queue.append(White[0])
White.remove(White[0])
frag += 1
new_geom = """\n"""
for i in Fragment[0]:
new_geom = new_geom + F[i].lstrip() + """\n"""
new_geom = new_geom + """--\n"""
for j in Fragment[1]:
new_geom = new_geom + F[j].lstrip() + """\n"""
new_geom = new_geom + """units angstrom\n"""
moleculenew = psi4.Molecule.create_molecule_from_string(new_geom)
moleculenew.set_name(molname)
moleculenew.update_geometry()
moleculenew.print_cluster()
psi4.print_out(""" Exiting auto_fragments\n""")
return moleculenew
def run_roa(name, **kwargs):
"""
Main driver for managing Raman Optical activity computations with
CC response theory.
Uses distributed finite differences approach -->
1. Sets up a database to keep track of running/finished/waiting
computations.
2. Generates separate input files for displaced geometries.
3. When all displacements are run, collects the necessary information
from each displaced computation, and computes final result.
"""
# Get list of omega values -> Make sure we only have one wavelength
# Catch this now before any real work gets done
omega = psi4.get_option('CCRESPONSE', 'OMEGA')
if len(omega) > 2:
raise Exception('ROA scattering can only be performed for one wavelength.')
else:
pass
psi4.print_out(
'Running ROA computation. Subdirectories for each '
'required displaced geometry have been created.\n\n')
dbno = 0
# Initialize database
db = shelve.open('database', writeback=True)
# Check if final result is in here
# ->if we have already computed roa, back up the dict
# ->copy it setting this flag to false and continue
if ('roa_computed' in db) and ( db['roa_computed'] ):
db2 = shelve.open('.database.bak{}'.format(dbno), writeback=True)
dbno += 1
for key,value in db.iteritems():
db2[key]=value
db2.close()
db['roa_computed'] = False
else:
db['roa_computed'] = False
if 'inputs_generated' not in db:
findif_response_utils.initialize_database(db,name,"roa", ["roa_tensor"])
# Generate input files
if not db['inputs_generated']:
findif_response_utils.generate_inputs(db,name)
# handled by helper db['inputs_generated'] = True
# Check job status
if db['inputs_generated'] and not db['jobs_complete']:
print('Checking status')
findif_response_utils.stat(db)
for job, status in db['job_status'].items():
print("{} --> {}".format(job, status))
# Compute ROA Scattering
if db['jobs_complete']:
mygauge = psi4.get_option('CCRESPONSE', 'GAUGE')
consider_gauge = {
'LENGTH': ['Length Gauge'],
'VELOCITY': ['Modified Velocity Gauge'],
'BOTH': ['Length Gauge', 'Modified Velocity Gauge']
}
gauge_list = ["{} Results".format(x) for x in consider_gauge[mygauge]]
# Gather data
dip_polar_list = findif_response_utils.collect_displaced_matrix_data(
db, 'Dipole Polarizability', 3)
opt_rot_list = [
x for x in (
findif_response_utils.collect_displaced_matrix_data(
db,
"Optical Rotation Tensor ({})".format(gauge),
3
)
for gauge in consider_gauge[mygauge]
)
]
dip_quad_polar_list = findif_response_utils.collect_displaced_matrix_data(
db, "Electric-Dipole/Quadrupole Polarizability", 9)
# Compute Scattering
# Run new function (src/bin/ccresponse/scatter.cc)
psi4.print_out('Running scatter function')
step = psi4.get_local_option('FINDIF', 'DISP_SIZE')
for g_idx, gauge in enumerate(opt_rot_list):
print('\n\n----------------------------------------------------------------------')
print('\t%%%%%%%%%% {} %%%%%%%%%%'.format(gauge_list[g_idx]))
print('----------------------------------------------------------------------\n\n')
psi4.print_out('\n\n----------------------------------------------------------------------\n')
psi4.print_out('\t%%%%%%%%%% {} %%%%%%%%%%\n'.format(gauge_list[g_idx]))
psi4.print_out('----------------------------------------------------------------------\n\n')
print('roa.py:85 I am not being passed a molecule, grabbing from global :(')
psi4.scatter(psi4.get_active_molecule(), step, dip_polar_list, gauge, dip_quad_polar_list)
db['roa_computed'] = True
db.close()
def __init__(self, msg):
PsiException.__init__(self, msg)
self.message = msg
psi4.print_out('\nCSXException: %s\n\n' % (msg))
def run_dftd3(self, func=None, dashlvl=None, dashparam=None, dertype=None, verbose=False):
"""Function to call Grimme's dftd3 program (http://toc.uni-muenster.de/DFTD3/)
to compute the -D correction of level *dashlvl* using parameters for
the functional *func*. The dictionary *dashparam* can be used to supply
a full set of dispersion parameters in the absense of *func* or to supply
individual overrides in the presence of *func*. Returns energy if *dertype* is 0,
gradient if *dertype* is 1, else tuple of energy and gradient if *dertype*
unspecified. The dftd3 executable must be independently compiled and found in
:envvar:`PATH` or :envvar:`PSIPATH`.
*self* may be either a qcdb.Molecule (sensibly) or a psi4.Molecule
(works b/c psi4.Molecule has been extended by this method py-side and
only public interface fns used) or a string that can be instantiated
into a qcdb.Molecule.
"""
# Create (if necessary) and update qcdb.Molecule
if isinstance(self, Molecule):
# called on a qcdb.Molecule
pass
elif isinstance(self, psi4.Molecule):
# called on a python export of a psi4.Molecule (py-side through Psi4's driver)
self.create_psi4_string_from_molecule()
elif isinstance(self, basestring):
# called on a string representation of a psi4.Molecule (c-side through psi4.Dispersion)
self = Molecule(self)
else:
raise ValidationError("""Argument mol must be psi4string or qcdb.Molecule""")
self.update_geometry()
# Validate arguments
dashlvl = dashlvl.lower()
dashlvl = dash_alias['-' + dashlvl][1:] if ('-' + dashlvl) in dash_alias.keys() else dashlvl
if dashlvl not in dashcoeff.keys():
raise ValidationError("""-D correction level %s is not available. Choose among %s.""" % (dashlvl, dashcoeff.keys()))
if dertype is None:
dertype = -1
elif der0th.match(str(dertype)):
dertype = 0
elif der1st.match(str(dertype)):
dertype = 1
elif der2nd.match(str(dertype)):
raise ValidationError('Requested derivative level \'dertype\' %s not valid for run_dftd3.' % (dertype))
else:
raise ValidationError('Requested derivative level \'dertype\' %s not valid for run_dftd3.' % (dertype))
if func is None:
if dashparam is None:
# defunct case
raise ValidationError("""Parameters for -D correction missing. Provide a func or a dashparam kwarg.""")
else:
# case where all param read from dashparam dict (which must have all correct keys)
func = 'custom'
dashcoeff[dashlvl][func] = {}
dashparam = dict((k.lower(), v) for k, v in dashparam.iteritems())
for key in dashcoeff[dashlvl]['b3lyp'].keys():
if key in dashparam.keys():
dashcoeff[dashlvl][func][key] = dashparam[key]
else:
raise ValidationError("""Parameter %s is missing from dashparam dict %s.""" % (key, dashparam))
else:
func = func.lower()
if func not in dashcoeff[dashlvl].keys():
raise ValidationError("""Functional %s is not available for -D level %s.""" % (func, dashlvl))
if dashparam is None:
# (normal) case where all param taken from dashcoeff above
pass
else:
# case where items in dashparam dict can override param taken from dashcoeff above
dashparam = dict((k.lower(), v) for k, v in dashparam.iteritems())
for key in dashcoeff[dashlvl]['b3lyp'].keys():
if key in dashparam.keys():
dashcoeff[dashlvl][func][key] = dashparam[key]
# Move ~/.dftd3par.<hostname> out of the way so it won't interfere
defaultfile = os.path.expanduser('~') + '/.dftd3par.' + socket.gethostname()
defmoved = False
if os.path.isfile(defaultfile):
os.rename(defaultfile, defaultfile + '_hide')
defmoved = True
# Find environment by merging PSIPATH and PATH environment variables
lenv = {
'PATH': ':'.join([os.path.abspath(x) for x in os.environ.get('PSIPATH', '').split(':') if x != '']) + \
':' + os.environ.get('PATH'),
'LD_LIBRARY_PATH': os.environ.get('LD_LIBRARY_PATH')
}
# Find out if running from Psi4 for scratch details and such
try:
psi4.version()
except NameError:
isP4regime = False
else:
isP4regime = True
# Setup unique scratch directory and move in
current_directory = os.getcwd()
if isP4regime:
psioh = psi4.IOManager.shared_object()
psio = psi4.IO.shared_object()
os.chdir(psioh.get_default_path())
dftd3_tmpdir = 'psi.' + str(os.getpid()) + '.' + psio.get_default_namespace() + \
'.dftd3.' + str(random.randint(0, 99999))
else:
dftd3_tmpdir = os.environ['HOME'] + os.sep + 'dftd3_' + str(random.randint(0, 99999))
if os.path.exists(dftd3_tmpdir) is False:
os.mkdir(dftd3_tmpdir)
os.chdir(dftd3_tmpdir)
# Write dftd3_parameters file that governs dispersion calc
paramcontents = dash_server(func, dashlvl, 'dftd3')
paramfile1 = 'dftd3_parameters' # older patched name
with open(paramfile1, 'w') as handle:
handle.write(paramcontents)
paramfile2 = '.dftd3par.local' # new mainline name
with open(paramfile2, 'w') as handle:
handle.write(paramcontents)
# Write dftd3_geometry file that supplies geometry to dispersion calc
numAtoms = self.natom()
geom = self.save_string_xyz()
reals = []
for line in geom.splitlines():
lline = line.split()
if len(lline) != 4:
continue
if lline[0] == 'Gh':
numAtoms -= 1
else:
reals.append(line)
geomtext = str(numAtoms) + '\n\n'
for line in reals:
geomtext += line.strip() + '\n'
geomfile = './dftd3_geometry.xyz'
with open(geomfile, 'w') as handle:
handle.write(geomtext)
# TODO somehow the variations on save_string_xyz and
# whether natom and chgmult does or doesn't get written
# have gotten all tangled. I fear this doesn't work
# the same btwn libmints and qcdb or for ghosts
# Call dftd3 program
command = ['dftd3', geomfile]
if dertype != 0:
command.append('-grad')
try:
dashout = subprocess.Popen(command, stdout=subprocess.PIPE, env=lenv)
except OSError as e:
raise ValidationError('Program dftd3 not found in path. %s' % e)
out, err = dashout.communicate()
# Parse output (could go further and break into E6, E8, E10 and Cn coeff)
success = False
for line in out.splitlines():
if re.match(' Edisp /kcal,au', line):
sline = line.split()
dashd = float(sline[3])
if re.match(' normal termination of dftd3', line):
success = True
if not success:
os.chdir(current_directory)
raise Dftd3Error("""Unsuccessful run. Possibly -D variant not available in dftd3 version.""")
# Parse grad output
if dertype != 0:
derivfile = './dftd3_gradient'
dfile = open(derivfile, 'r')
dashdderiv = []
for line in geom.splitlines():
lline = line.split()
if len(lline) != 4:
continue
if lline[0] == 'Gh':
dashdderiv.append([0.0, 0.0, 0.0])
else:
dashdderiv.append([float(x.replace('D', 'E')) for x in dfile.readline().split()])
dfile.close()
if len(dashdderiv) != self.natom():
raise ValidationError('Program dftd3 gradient file has %d atoms- %d expected.' % \
(len(dashdderiv), self.natom()))
# Prepare results for Psi4
if isP4regime and dertype != 0:
psi4.set_variable('DISPERSION CORRECTION ENERGY', dashd)
psi_dashdderiv = psi4.Matrix(self.natom(), 3)
psi_dashdderiv.set(dashdderiv)
# Print program output to file if verbose
if isP4regime:
verbose = True if psi4.get_option('SCF', 'PRINT') >= 3 else False
if verbose:
text = '\n ==> DFTD3 Output <==\n'
text += out
if dertype != 0:
with open(derivfile, 'r') as handle:
text += handle.read().replace('D', 'E')
text += '\n'
if isP4regime:
psi4.print_out(text)
else:
print(text)
# Clean up files and remove scratch directory
os.unlink(paramfile1)
os.unlink(paramfile2)
os.unlink(geomfile)
if dertype != 0:
os.unlink(derivfile)
if defmoved is True:
os.rename(defaultfile + '_hide', defaultfile)
os.chdir('..')
try:
shutil.rmtree(dftd3_tmpdir)
except OSError as e:
ValidationError('Unable to remove dftd3 temporary directory %s' % e)
os.chdir(current_directory)
# return -D & d(-D)/dx
if dertype == -1:
return dashd, dashdderiv
elif dertype == 0:
return dashd
elif dertype == 1:
return psi_dashdderiv
def run_dftd3(self,
func=None,
dashlvl=None,
dashparam=None,
dertype=None,
verbose=False):
"""Function to call Grimme's dftd3 program (http://toc.uni-muenster.de/DFTD3/)
to compute the -D correction of level *dashlvl* using parameters for
the functional *func*. The dictionary *dashparam* can be used to supply
a full set of dispersion parameters in the absense of *func* or to supply
individual overrides in the presence of *func*. Returns energy if *dertype* is 0,
gradient if *dertype* is 1, else tuple of energy and gradient if *dertype*
unspecified. The dftd3 executable must be independently compiled and found in
:envvar:`PATH` or :envvar:`PSIPATH`.
*self* may be either a qcdb.Molecule (sensibly) or a psi4.Molecule
(works b/c psi4.Molecule has been extended by this method py-side and
only public interface fns used) or a string that can be instantiated
into a qcdb.Molecule.
"""
# Create (if necessary) and update qcdb.Molecule
if isinstance(self, Molecule):
# called on a qcdb.Molecule
pass
elif isinstance(self, psi4.Molecule):
# called on a python export of a psi4.Molecule (py-side through Psi4's driver)
self.create_psi4_string_from_molecule()
elif isinstance(self, basestring):
# called on a string representation of a psi4.Molecule (c-side through psi4.Dispersion)
self = Molecule(self)
else:
raise ValidationError(
"""Argument mol must be psi4string or qcdb.Molecule""")
self.update_geometry()
# Validate arguments
dashlvl = dashlvl.lower()
dashlvl = dash_alias['-' + dashlvl][1:] if (
'-' + dashlvl) in dash_alias.keys() else dashlvl
if dashlvl not in dashcoeff.keys():
raise ValidationError(
"""-D correction level %s is not available. Choose among %s.""" %
(dashlvl, dashcoeff.keys()))
if dertype is None:
dertype = -1
elif der0th.match(str(dertype)):
dertype = 0
elif der1st.match(str(dertype)):
dertype = 1
elif der2nd.match(str(dertype)):
raise ValidationError(
'Requested derivative level \'dertype\' %s not valid for run_dftd3.'
% (dertype))
else:
raise ValidationError(
'Requested derivative level \'dertype\' %s not valid for run_dftd3.'
% (dertype))
if func is None:
if dashparam is None:
# defunct case
raise ValidationError(
"""Parameters for -D correction missing. Provide a func or a dashparam kwarg."""
)
else:
# case where all param read from dashparam dict (which must have all correct keys)
func = 'custom'
dashcoeff[dashlvl][func] = {}
dashparam = dict((k.lower(), v) for k, v in dashparam.iteritems())
for key in dashcoeff[dashlvl]['b3lyp'].keys():
if key in dashparam.keys():
dashcoeff[dashlvl][func][key] = dashparam[key]
else:
raise ValidationError(
"""Parameter %s is missing from dashparam dict %s.""" %
(key, dashparam))
else:
func = func.lower()
if func not in dashcoeff[dashlvl].keys():
raise ValidationError(
"""Functional %s is not available for -D level %s.""" %
(func, dashlvl))
if dashparam is None:
# (normal) case where all param taken from dashcoeff above
pass
else:
# case where items in dashparam dict can override param taken from dashcoeff above
dashparam = dict((k.lower(), v) for k, v in dashparam.iteritems())
for key in dashcoeff[dashlvl]['b3lyp'].keys():
if key in dashparam.keys():
dashcoeff[dashlvl][func][key] = dashparam[key]
# Move ~/.dftd3par.<hostname> out of the way so it won't interfere
defaultfile = os.path.expanduser(
'~') + '/.dftd3par.' + socket.gethostname()
defmoved = False
if os.path.isfile(defaultfile):
os.rename(defaultfile, defaultfile + '_hide')
defmoved = True
# Find environment by merging PSIPATH and PATH environment variables
lenv = {
'PATH': ':'.join([os.path.abspath(x) for x in os.environ.get('PSIPATH', '').split(':') if x != '']) + \
':' + os.environ.get('PATH'),
'LD_LIBRARY_PATH': os.environ.get('LD_LIBRARY_PATH')
}
# Filter out None values as subprocess will fault on them
lenv = {k: v for k, v in lenv.items() if v is not None}
# Find out if running from Psi4 for scratch details and such
try:
psi4.version()
except NameError:
isP4regime = False
else:
isP4regime = True
# Setup unique scratch directory and move in
current_directory = os.getcwd()
if isP4regime:
psioh = psi4.IOManager.shared_object()
psio = psi4.IO.shared_object()
os.chdir(psioh.get_default_path())
dftd3_tmpdir = 'psi.' + str(os.getpid()) + '.' + psio.get_default_namespace() + \
'.dftd3.' + str(random.randint(0, 99999))
else:
dftd3_tmpdir = os.environ['HOME'] + os.sep + 'dftd3_' + str(
random.randint(0, 99999))
if os.path.exists(dftd3_tmpdir) is False:
os.mkdir(dftd3_tmpdir)
os.chdir(dftd3_tmpdir)
# Write dftd3_parameters file that governs dispersion calc
paramcontents = dash_server(func, dashlvl, 'dftd3')
paramfile1 = 'dftd3_parameters' # older patched name
with open(paramfile1, 'w') as handle:
handle.write(paramcontents)
paramfile2 = '.dftd3par.local' # new mainline name
with open(paramfile2, 'w') as handle:
handle.write(paramcontents)
# Write dftd3_geometry file that supplies geometry to dispersion calc
numAtoms = self.natom()
geom = self.save_string_xyz()
reals = []
for line in geom.splitlines():
lline = line.split()
if len(lline) != 4:
continue
if lline[0] == 'Gh':
numAtoms -= 1
else:
reals.append(line)
geomtext = str(numAtoms) + '\n\n'
for line in reals:
geomtext += line.strip() + '\n'
geomfile = './dftd3_geometry.xyz'
with open(geomfile, 'w') as handle:
handle.write(geomtext)
# TODO somehow the variations on save_string_xyz and
# whether natom and chgmult does or doesn't get written
# have gotten all tangled. I fear this doesn't work
# the same btwn libmints and qcdb or for ghosts
# Call dftd3 program
command = ['dftd3', geomfile]
if dertype != 0:
command.append('-grad')
try:
dashout = subprocess.Popen(command, stdout=subprocess.PIPE, env=lenv)
except OSError as e:
raise ValidationError('Program dftd3 not found in path. %s' % e)
out, err = dashout.communicate()
# Parse output (could go further and break into E6, E8, E10 and Cn coeff)
success = False
for line in out.splitlines():
if re.match(' Edisp /kcal,au', line):
sline = line.split()
dashd = float(sline[3])
if re.match(' normal termination of dftd3', line):
success = True
if not success:
os.chdir(current_directory)
raise Dftd3Error(
"""Unsuccessful run. Possibly -D variant not available in dftd3 version."""
)
# Parse grad output
if dertype != 0:
derivfile = './dftd3_gradient'
dfile = open(derivfile, 'r')
dashdderiv = []
for line in geom.splitlines():
lline = line.split()
if len(lline) != 4:
continue
if lline[0] == 'Gh':
dashdderiv.append([0.0, 0.0, 0.0])
else:
dashdderiv.append([
float(x.replace('D', 'E'))
for x in dfile.readline().split()
])
dfile.close()
if len(dashdderiv) != self.natom():
raise ValidationError('Program dftd3 gradient file has %d atoms- %d expected.' % \
(len(dashdderiv), self.natom()))
# Prepare results for Psi4
if isP4regime and dertype != 0:
psi4.set_variable('DISPERSION CORRECTION ENERGY', dashd)
psi_dashdderiv = psi4.Matrix(self.natom(), 3)
psi_dashdderiv.set(dashdderiv)
# Print program output to file if verbose
if isP4regime:
verbose = True if psi4.get_option('SCF', 'PRINT') >= 3 else False
if verbose:
text = '\n ==> DFTD3 Output <==\n'
text += out
if dertype != 0:
with open(derivfile, 'r') as handle:
text += handle.read().replace('D', 'E')
text += '\n'
if isP4regime:
psi4.print_out(text)
else:
print(text)
# Clean up files and remove scratch directory
os.unlink(paramfile1)
os.unlink(paramfile2)
os.unlink(geomfile)
if dertype != 0:
os.unlink(derivfile)
if defmoved is True:
os.rename(defaultfile + '_hide', defaultfile)
os.chdir('..')
try:
shutil.rmtree(dftd3_tmpdir)
except OSError as e:
ValidationError('Unable to remove dftd3 temporary directory %s' % e)
os.chdir(current_directory)
# return -D & d(-D)/dx
if dertype == -1:
return dashd, dashdderiv
elif dertype == 0:
return dashd
elif dertype == 1:
return psi_dashdderiv
def run_dftd3(self, func=None, dashlvl=None, dashparam=None, dertype=None):
"""Function to call Grimme's dftd3 program (http://toc.uni-muenster.de/DFTD3/)
to compute the -D correction of level *dashlvl* using parameters for
the functional *func*. The dictionary *dashparam* can be used to supply
a full set of dispersion parameters in the absense of *func* or to supply
individual overrides in the presence of *func*. Returns energy if *dertype* is 0,
gradient if *dertype* is 1, else tuple of energy and gradient if *dertype*
unspecified. The dftd3 executable must be independently compiled and found in
:envvar:`PATH`.
"""
# Validate arguments
if self is None:
self = psi4.get_active_molecule()
dashlvl = dashlvl.lower()
dashlvl = dash_alias['-' + dashlvl][1:] if ('-' + dashlvl) in dash_alias.keys() else dashlvl
if dashlvl not in dashcoeff.keys():
raise ValidationError("""-D correction level %s is not available. Choose among %s.""" % (dashlvl, dashcoeff.keys()))
if dertype is None:
dertype = -1
elif der0th.match(str(dertype)):
dertype = 0
elif der1st.match(str(dertype)):
dertype = 1
elif der2nd.match(str(dertype)):
raise ValidationError('Requested derivative level \'dertype\' %s not valid for run_dftd3.' % (dertype))
else:
raise ValidationError('Requested derivative level \'dertype\' %s not valid for run_dftd3.' % (dertype))
if func is None:
if dashparam is None:
# defunct case
raise ValidationError("""Parameters for -D correction missing. Provide a func or a dashparam kwarg.""")
else:
# case where all param read from dashparam dict (which must have all correct keys)
func = 'custom'
dashcoeff[dashlvl][func] = {}
dashparam = dict((k.lower(), v) for k, v in dashparam.items())
for key in dashcoeff[dashlvl]['b3lyp'].keys():
if key in dashparam.keys():
dashcoeff[dashlvl][func][key] = dashparam[key]
else:
raise ValidationError("""Parameter %s is missing from dashparam dict %s.""" % (key, dashparam))
else:
func = func.lower()
if func not in dashcoeff[dashlvl].keys():
raise ValidationError("""Functional %s is not available for -D level %s.""" % (func, dashlvl))
if dashparam is None:
# (normal) case where all param taken from dashcoeff above
pass
else:
# case where items in dashparam dict can override param taken from dashcoeff above
dashparam = dict((k.lower(), v) for k, v in dashparam.items())
for key in dashcoeff[dashlvl]['b3lyp'].keys():
if key in dashparam.keys():
dashcoeff[dashlvl][func][key] = dashparam[key]
# Move ~/.dftd3par.<hostname> out of the way so it won't interfere
defaultfile = os.path.expanduser('~') + '/.dftd3par.' + socket.gethostname()
defmoved = False
if os.path.isfile(defaultfile):
os.rename(defaultfile, defaultfile + '_hide')
defmoved = True
# Setup unique scratch directory and move in
current_directory = os.getcwd()
psioh = psi4.IOManager.shared_object()
psio = psi4.IO.shared_object()
os.chdir(psioh.get_default_path())
dftd3_tmpdir = 'psi.' + str(os.getpid()) + '.' + psio.get_default_namespace() + \
'.dftd3.' + str(random.randint(0, 99999))
if os.path.exists(dftd3_tmpdir) is False:
os.mkdir(dftd3_tmpdir)
os.chdir(dftd3_tmpdir)
# Write dftd3_parameters file that governs dispersion calc
paramfile = './dftd3_parameters'
pfile = open(paramfile, 'w')
pfile.write(dash_server(func, dashlvl, 'dftd3'))
pfile.close()
# Write dftd3_geometry file that supplies geometry to dispersion calc
geomfile = './dftd3_geometry.xyz'
gfile = open(geomfile, 'w')
numAtoms = self.natom()
geom = self.save_string_xyz()
reals = []
for line in geom.splitlines():
if line.split()[0] == 'Gh':
numAtoms -= 1
else:
reals.append(line)
gfile.write(str(numAtoms)+'\n')
for line in reals:
gfile.write(line.strip()+'\n')
gfile.close()
# Call dftd3 program
try:
dashout = subprocess.Popen(['dftd3', geomfile, '-grad'], stdout=subprocess.PIPE)
except OSError:
raise ValidationError('Program dftd3 not found in path.')
out, err = dashout.communicate()
# Parse output (could go further and break into E6, E8, E10 and Cn coeff)
success = False
for line in out.splitlines():
# communicate in python 3 returns a byte array rather than a string.
# Convert to string--only need a simple encoding for comparison.
line = line.decode('utf-8')
if re.match(' Edisp /kcal,au', line):
sline = line.split()
dashd = float(sline[3])
if re.match(' normal termination of dftd3', line):
success = True
if not success:
raise ValidationError('Program dftd3 did not complete successfully.')
# Parse grad output
derivfile = './dftd3_gradient'
dfile = open(derivfile, 'r')
dashdderiv = []
i = 0
for line in geom.splitlines():
if i == 0:
i += 1
else:
if line.split()[0] == 'Gh':
dashdderiv.append([0.0, 0.0, 0.0])
else:
temp = dfile.readline()
dashdderiv.append([float(x.replace('D', 'E')) for x in temp.split()])
dfile.close()
if len(dashdderiv) != self.natom():
raise ValidationError('Program dftd3 gradient file has %d atoms- %d expected.' % \
(len(dashdderiv), self.natom()))
psi_dashdderiv = psi4.Matrix(self.natom(), 3)
psi_dashdderiv.set(dashdderiv)
# Print program output to file if verbose
verbose = psi4.get_option('SCF', 'PRINT')
if verbose >= 3:
psi4.print_out('\n ==> DFTD3 Output <==\n')
psi4.print_out(out)
dfile = open(derivfile, 'r')
psi4.print_out(dfile.read().replace('D', 'E'))
dfile.close()
psi4.print_out('\n')
# Clean up files and remove scratch directory
os.unlink(paramfile)
os.unlink(geomfile)
os.unlink(derivfile)
if defmoved is True:
os.rename(defaultfile + '_hide', defaultfile)
os.chdir('..')
try:
shutil.rmtree(dftd3_tmpdir)
except OSError as e:
ValidationError('Unable to remove dftd3 temporary directory %s' % e, file=sys.stderr)
os.chdir(current_directory)
# return -D & d(-D)/dx
psi4.set_variable('DISPERSION CORRECTION ENERGY', dashd)
if dertype == -1:
return dashd, dashdderiv
elif dertype == 0:
return dashd
elif dertype == 1:
return psi_dashdderiv
def frac_nuke(molecule, **kwargs):
kwargs = p4util.kwargs_lower(kwargs)
# The molecule is required, and should be the neutral species
molecule.update_geometry()
charge0 = molecule.molecular_charge()
mult0 = molecule.multiplicity()
# By default, we start the frac procedure on the 25th iteration
# when not reading a previous guess
frac_start = kwargs.get('frac_start', 25)
# By default, we occupy by tenths of electrons
foccs = kwargs.get('foccs', [1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.0])
# By default, H**O and LUMO are both in alpha
N = 0;
for A in range(molecule.natom()):
N += molecule.Z(A)
N -= charge0
N = int(N)
Nb = int((N - mult0 + 1) / 2)
Na = int(N - Nb)
charge = charge0
mult = mult0
# By default, nuke all the electrons
Nmin = 0;
if ('nmax' in kwargs):
Nmin = N - int(kwargs['nmax'])
# By default, DIIS in FRAC (1.0 occupation is always DIIS'd)
frac_diis = kwargs.get('frac_diis', True)
# By default, drop the files to the molecule's name
root = kwargs.get('filename', molecule.name())
traverse_filename = root + '.traverse.dat'
stats_filename = root + '.stats.dat'
# => Traverse <= #
psi4.set_global_option("DF_INTS_IO", "SAVE")
Ns = []
energies = []
potentials = []
convs = []
stats = []
# Run one SCF to burn things in
E, wfn= energy('scf', return_wfn=True, molecule=molecule, **kwargs)
# Determine H**O
eps_a = wfn.epsilon_a()
eps_b = wfn.epsilon_b()
if Na == Nb:
H**O = -Nb
elif Nb == 0:
H**O = Na
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if E_a >= E_b:
H**O = Na
else:
H**O = -Nb
stats.append("""\t%6d %6d %6d %6d %6d %6d\n""" % (N, Na, Nb, charge, mult, H**O))
if H**O > 0:
Na = Na - 1
else:
Nb = Nb - 1
charge = charge + 1
mult = Na - Nb + 1
psi4.set_global_option("DF_INTS_IO", "LOAD")
psi4.set_global_option("FRAC_START", frac_start)
psi4.set_global_option("FRAC_RENORMALIZE", True)
# Nuke 'em Rico!
for Nintegral in range(N, Nmin, -1):
# Nuke the current H**O
for occ in foccs:
psi4.set_global_option("FRAC_OCC", [H**O])
psi4.set_global_option("FRAC_VAL", [occ])
E, wfn = energy('scf', return_wfn=True, molecule=molecule, **kwargs)
C = 1
if E == 0.0:
E = psi4.get_variable('SCF ITERATION ENERGY')
C = 0
if H**O > 0:
eps = wfn.epsilon_a()
potentials.append(eps[H**O - 1])
else:
eps = wfn.epsilon_b()
potentials.append(eps[-H**O - 1])
Ns.append(Nintegral + occ - 1.0)
energies.append(E)
convs.append(C)
psi4.set_global_option("FRAC_START", 2)
psi4.set_global_option("FRAC_LOAD", True)
psi4.set_global_option("FRAC_DIIS", frac_diis)
psi4.set_global_option("GUESS", "READ")
# Set the next charge/mult
molecule.set_molecular_charge(charge)
molecule.set_multiplicity(mult)
# Determine H**O
print('DGAS: What ref should this point to?')
#ref = psi4.legacy_wavefunction()
eps_a = wfn.epsilon_a()
eps_b = wfn.epsilon_b()
if Na == Nb:
H**O = -Nb
elif Nb == 0:
H**O = Na
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if E_a >= E_b:
H**O = Na
else:
H**O = -Nb
stats.append("""\t%6d %6d %6d %6d %6d %6d\n""" % (Nintegral-1, Na, Nb, charge, mult, H**O))
if H**O > 0:
Na = Na - 1
else:
Nb = Nb - 1
charge = charge + 1
mult = Na - Nb + 1
psi4.set_global_option("DF_INTS_IO", "NONE")
# => Print the results out <= #
E = {}
psi4.print_out("""\n ==> Fractional Occupation Nuke Results <==\n\n""")
psi4.print_out("""\t%-11s %-24s %-24s %11s\n""" % ('N', 'Energy', 'H**O Energy', 'Converged'))
for k in range(len(Ns)):
psi4.print_out("""\t%11.3E %24.16E %24.16E %11d\n""" % (Ns[k], energies[k], potentials[k], convs[k]))
E[Ns[k]] = energies[k]
psi4.print_out('\n')
psi4.print_out("""\t%6s %6s %6s %6s %6s %6s\n""" % ('N', 'Na', 'Nb', 'Charge', 'Mult', 'H**O'))
for line in stats:
psi4.print_out(line)
psi4.print_out('\n\t"You shoot a nuke down a bug hole, you got a lot of dead bugs"\n')
psi4.print_out('\t\t\t-Starship Troopers\n')
# Drop the files out
fh = open(traverse_filename, 'w')
fh.write("""\t%-11s %-24s %-24s %11s\n""" % ('N', 'Energy', 'H**O Energy', 'Converged'))
for k in range(len(Ns)):
fh.write("""\t%11.3E %24.16E %24.16E %11d\n""" % (Ns[k], energies[k], potentials[k], convs[k]))
fh.close()
fh = open(stats_filename, 'w')
fh.write("""\t%6s %6s %6s %6s %6s %6s\n""" % ('N', 'Na', 'Nb', 'Charge', 'Mult', 'H**O'))
for line in stats:
fh.write(line)
fh.close()
# Properly, should clone molecule but since not returned and easy to unblemish,
molecule.set_molecular_charge(charge0)
molecule.set_multiplicity(mult0)
return E
def _nbody_gufunc(func, method_string, **kwargs):
"""
Computes the nbody interaction energy, gradient, or Hessian depending on input.
Parameters
----------
func : python function
Python function that accepts method_string and a molecule and returns a energy, gradient, or Hessian.
method_string : str
Lowername to be passed to function
molecule : psi4.Molecule (default: Global Molecule)
Molecule to use in all computations
return_wfn : bool (default: False)
Return a wavefunction or not
bsse_type : str or list (default: None, this function is not called)
Type of BSSE correction to compute: CP, NoCP, or VMFC. The first in this list is returned by this function.
max_nbody : int
Maximum n-body to compute, cannot exceede the number of fragments in the moleucle
ptype : str
Type of the procedure passed in
return_total_data : bool (default: False)
If True returns the total data (energy/gradient/etc) of the system otherwise returns interaction data
Returns
-------
data : return type of func
The interaction data
wfn : psi4.Wavefunction (optional)
A wavefunction with energy/gradient/hessian set appropriotely. This wavefunction also contains
Notes
-----
This is a generalized univeral function for compute interaction quantities.
Examples
--------
"""
### ==> Parse some kwargs <==
kwargs = p4util.kwargs_lower(kwargs)
return_wfn = kwargs.pop('return_wfn', False)
ptype = kwargs.pop('ptype', None)
return_total_data = kwargs.pop('return_total_data', False)
molecule = kwargs.pop('molecule', psi4.get_active_molecule())
molecule.update_geometry()
psi4.clean_variables()
if ptype not in ['energy', 'gradient', 'hessian']:
raise ValidationError(
"""N-Body driver: The ptype '%s' is not regonized.""" % ptype)
# Figure out BSSE types
do_cp = False
do_nocp = False
do_vmfc = False
return_method = False
# Must be passed bsse_type
bsse_type_list = kwargs.pop('bsse_type')
if bsse_type_list is None:
raise ValidationError("N-Body GUFunc: Must pass a bsse_type")
if not isinstance(bsse_type_list, list):
bsse_type_list = [bsse_type_list]
for num, btype in enumerate(bsse_type_list):
if btype.lower() == 'cp':
do_cp = True
if (num == 0): return_method = 'cp'
elif btype.lower() == 'nocp':
do_nocp = True
if (num == 0): return_method = 'nocp'
elif btype.lower() == 'vmfc':
do_vmfc = True
if (num == 0): return_method = 'vmfc'
else:
raise ValidationError(
"N-Body GUFunc: bsse_type '%s' is not recognized" %
btype.lower())
max_nbody = kwargs.get('max_nbody', -1)
max_frag = molecule.nfragments()
if max_nbody == -1:
max_nbody = molecule.nfragments()
else:
max_nbody = min(max_nbody, max_frag)
# What levels do we need?
nbody_range = range(1, max_nbody + 1)
fragment_range = range(1, max_frag + 1)
# Flip this off for now, needs more testing
# If we are doing CP lets save them integrals
#if 'cp' in bsse_type_list and (len(bsse_type_list) == 1):
# # Set to save RI integrals for repeated full-basis computations
# ri_ints_io = psi4.get_global_option('DF_INTS_IO')
# # inquire if above at all applies to dfmp2 or just scf
# psi4.set_global_option('DF_INTS_IO', 'SAVE')
# psioh = psi4.IOManager.shared_object()
# psioh.set_specific_retention(97, True)
bsse_str = bsse_type_list[0]
if len(bsse_type_list) > 1:
bsse_str = str(bsse_type_list)
psi4.print_out("\n\n")
psi4.print_out(" ===> N-Body Interaction Abacus <===\n")
psi4.print_out(" BSSE Treatment: %s\n" %
bsse_str)
cp_compute_list = {x: set() for x in nbody_range}
nocp_compute_list = {x: set() for x in nbody_range}
vmfc_compute_list = {x: set() for x in nbody_range}
vmfc_level_list = {x: set()
for x in nbody_range
} # Need to sum something slightly different
# Build up compute sets
if do_cp:
# Everything is in dimer basis
basis_tuple = tuple(fragment_range)
for nbody in nbody_range:
for x in it.combinations(fragment_range, nbody):
cp_compute_list[nbody].add((x, basis_tuple))
if do_nocp:
# Everything in monomer basis
for nbody in nbody_range:
for x in it.combinations(fragment_range, nbody):
nocp_compute_list[nbody].add((x, x))
if do_vmfc:
# Like a CP for all combinations of pairs or greater
for nbody in nbody_range:
for cp_combos in it.combinations(fragment_range, nbody):
basis_tuple = tuple(cp_combos)
for interior_nbody in nbody_range:
for x in it.combinations(cp_combos, interior_nbody):
combo_tuple = (x, basis_tuple)
vmfc_compute_list[interior_nbody].add(combo_tuple)
vmfc_level_list[len(basis_tuple)].add(combo_tuple)
# Build a comprehensive compute_range
compute_list = {x: set() for x in nbody_range}
for n in nbody_range:
compute_list[n] |= cp_compute_list[n]
compute_list[n] |= nocp_compute_list[n]
compute_list[n] |= vmfc_compute_list[n]
psi4.print_out(" Number of %d-body computations: %d\n" %
(n, len(compute_list[n])))
# Build size and slices dictionaries
fragment_size_dict = {
frag: molecule.extract_subsets(frag).natom()
for frag in range(1, max_frag + 1)
}
start = 0
fragment_slice_dict = {}
for k, v in fragment_size_dict.items():
fragment_slice_dict[k] = slice(start, start + v)
start += v
molecule_total_atoms = sum(fragment_size_dict.values())
# Now compute the energies
energies_dict = {}
ptype_dict = {}
for n in compute_list.keys():
psi4.print_out(
"\n ==> N-Body: Now computing %d-body complexes <==\n\n" % n)
print("\n ==> N-Body: Now computing %d-body complexes <==\n" % n)
total = len(compute_list[n])
for num, pair in enumerate(compute_list[n]):
psi4.print_out(
"\n N-Body: Computing complex (%d/%d) with fragments %s in the basis of fragments %s.\n\n"
% (num + 1, total, str(pair[0]), str(pair[1])))
ghost = list(set(pair[1]) - set(pair[0]))
current_mol = molecule.extract_subsets(list(pair[0]), ghost)
ptype_dict[pair] = func(method_string,
molecule=current_mol,
**kwargs)
energies_dict[pair] = psi4.get_variable("CURRENT ENERGY")
psi4.print_out(
"\n N-Body: Complex Energy (fragments = %s, basis = %s: %20.14f)\n"
% (str(pair[0]), str(pair[1]), energies_dict[pair]))
# Flip this off for now, needs more testing
#if 'cp' in bsse_type_list and (len(bsse_type_list) == 1):
# psi4.set_global_option('DF_INTS_IO', 'LOAD')
psi4.clean()
# Final dictionaries
cp_energy_by_level = {n: 0.0 for n in nbody_range}
nocp_energy_by_level = {n: 0.0 for n in nbody_range}
cp_energy_body_dict = {n: 0.0 for n in nbody_range}
nocp_energy_body_dict = {n: 0.0 for n in nbody_range}
vmfc_energy_body_dict = {n: 0.0 for n in nbody_range}
# Build out ptype dictionaries if needed
if ptype != 'energy':
if ptype == 'gradient':
arr_shape = (molecule_total_atoms, 3)
elif ptype == 'hessian':
arr_shape = (molecule_total_atoms * 3, molecule_total_atoms * 3)
else:
raise KeyError("N-Body: ptype '%s' not recognized" % ptype)
cp_ptype_by_level = {n: np.zeros(arr_shape) for n in nbody_range}
nocp_ptype_by_level = {n: np.zeros(arr_shape) for n in nbody_range}
cp_ptype_body_dict = {n: np.zeros(arr_shape) for n in nbody_range}
nocp_ptype_body_dict = {n: np.zeros(arr_shape) for n in nbody_range}
vmfc_ptype_body_dict = {n: np.zeros(arr_shape) for n in nbody_range}
else:
cp_ptype_by_level, cp_ptype_body_dict = None, None
nocp_ptype_by_level, nocp_ptype_body_dict = None, None
vmfc_ptype_body_dict = None
# Sum up all of the levels
for n in nbody_range:
# Energy
cp_energy_by_level[n] = sum(energies_dict[v]
for v in cp_compute_list[n])
nocp_energy_by_level[n] = sum(energies_dict[v]
for v in nocp_compute_list[n])
# Special vmfc case
if n > 1:
vmfc_energy_body_dict[n] = vmfc_energy_body_dict[n - 1]
for tup in vmfc_level_list[n]:
vmfc_energy_body_dict[n] += (
(-1)**(n - len(tup[0]))) * energies_dict[tup]
# Do ptype
if ptype != 'energy':
_sum_cluster_ptype_data(ptype, ptype_dict, cp_compute_list[n],
fragment_slice_dict, fragment_size_dict,
cp_ptype_by_level[n])
_sum_cluster_ptype_data(ptype, ptype_dict, nocp_compute_list[n],
fragment_slice_dict, fragment_size_dict,
nocp_ptype_by_level[n])
_sum_cluster_ptype_data(ptype,
ptype_dict,
vmfc_level_list[n],
fragment_slice_dict,
fragment_size_dict,
vmfc_ptype_by_level[n],
vmfc=True)
# Compute cp energy and ptype
if do_cp:
for n in nbody_range:
if n == max_frag:
cp_energy_body_dict[n] = cp_energy_by_level[n]
if ptype != 'energy':
cp_ptype_body_dict[n][:] = cp_ptype_by_level[n]
continue
for k in range(1, n + 1):
take_nk = nCr(max_frag - k - 1, n - k)
sign = ((-1)**(n - k))
value = cp_energy_by_level[k]
cp_energy_body_dict[n] += take_nk * sign * value
if ptype != 'energy':
value = cp_ptype_by_level[k]
cp_ptype_body_dict[n] += take_nk * sign * value
_print_nbody_energy(cp_energy_body_dict, "Counterpoise Corrected (CP)")
cp_interaction_energy = cp_energy_body_dict[
max_nbody] - cp_energy_body_dict[1]
psi4.set_variable('Counterpoise Corrected Total Energy',
cp_energy_body_dict[max_nbody])
psi4.set_variable('Counterpoise Corrected Interaction Energy',
cp_interaction_energy)
for n in nbody_range[1:]:
var_key = 'CP-CORRECTED %d-BODY INTERACTION ENERGY' % n
psi4.set_variable(var_key,
cp_energy_body_dict[n] - cp_energy_body_dict[1])
# Compute nocp energy and ptype
if do_nocp:
for n in nbody_range:
if n == max_frag:
nocp_energy_body_dict[n] = nocp_energy_by_level[n]
if ptype != 'energy':
nocp_ptype_body_dict[n][:] = nocp_ptype_by_level[n]
continue
for k in range(1, n + 1):
take_nk = nCr(max_frag - k - 1, n - k)
sign = ((-1)**(n - k))
value = nocp_energy_by_level[k]
nocp_energy_body_dict[n] += take_nk * sign * value
if ptype != 'energy':
value = nocp_ptype_by_level[k]
nocp_ptype_body_dict[n] += take_nk * sign * value
_print_nbody_energy(nocp_energy_body_dict,
"Non-Counterpoise Corrected (NoCP)")
nocp_interaction_energy = nocp_energy_body_dict[
max_nbody] - nocp_energy_body_dict[1]
psi4.set_variable('Non-Counterpoise Corrected Total Energy',
nocp_energy_body_dict[max_nbody])
psi4.set_variable('Non-Counterpoise Corrected Interaction Energy',
nocp_interaction_energy)
for n in nbody_range[1:]:
var_key = 'NOCP-CORRECTED %d-BODY INTERACTION ENERGY' % n
psi4.set_variable(
var_key, nocp_energy_body_dict[n] - nocp_energy_body_dict[1])
# Compute vmfc energy and ptype
if do_vmfc:
_print_nbody_energy(vmfc_energy_body_dict,
"Valiron-Mayer Function Couterpoise (VMFC)")
vmfc_interaction_energy = vmfc_energy_body_dict[
max_nbody] - vmfc_energy_body_dict[1]
psi4.set_variable('Valiron-Mayer Function Couterpoise Total Energy',
vmfc_energy_body_dict[max_nbody])
psi4.set_variable(
'Valiron-Mayer Function Couterpoise Interaction Energy',
vmfc_interaction_energy)
for n in nbody_range[1:]:
var_key = 'VMFC-CORRECTED %d-BODY INTERACTION ENERGY' % n
psi4.set_variable(
var_key, vmfc_energy_body_dict[n] - vmfc_energy_body_dict[1])
if return_method == 'cp':
ptype_body_dict = cp_ptype_body_dict
energy_body_dict = cp_energy_body_dict
elif return_method == 'nocp':
ptype_body_dict = nocp_ptype_body_dict
energy_body_dict = nocp_energy_body_dict
elif return_method == 'vmfc':
ptype_body_dict = vmfc_ptype_body_dict
energy_body_dict = vmfc_energy_body_dict
else:
raise ValidationError(
"N-Body Wrapper: Invalid return type. Should never be here, please post this error on github."
)
# Figure out and build return types
if return_total_data:
ret_energy = energy_body_dict[max_nbody]
else:
ret_energy = energy_body_dict[max_nbody]
ret_energy -= energy_body_dict[1]
if ptype != 'energy':
if return_total_data:
np_final_ptype = ptype_body_dict[max_nbody].copy()
else:
np_final_ptype = ptype_body_dict[max_nbody].copy()
np_final_ptype -= ptype_body_dict[1]
ret_ptype = psi4.Matrix(*np_cp_final_ptype.shape)
ret_ptype_view = np.asarray(final_ptype)
ret_ptype_view[:] = np_final_ptype
else:
ret_ptype = ret_energy
# Build and set a wavefunction
wfn = psi4.new_wavefunction(molecule, 'sto-3g')
wfn.nbody_energy = energies_dict
wfn.nbody_ptype = ptype_dict
wfn.nbody_body_energy = energy_body_dict
wfn.nbody_body_ptype = ptype_body_dict
if ptype == 'gradient':
wfn.set_gradient(ret_ptype)
elif ptype == 'hessian':
wfn.set_hessian(ret_ptype)
psi4.set_variable("CURRENT ENERGY", ret_energy)
if return_wfn:
return (ret_ptype, wfn)
else:
return ret_ptype
def frac_traverse(molecule, **kwargs):
kwargs = p4util.kwargs_lower(kwargs)
# The molecule is required, and should be the neutral species
molecule.update_geometry()
charge0 = molecule.molecular_charge()
mult0 = molecule.multiplicity()
chargep = charge0 + 1
chargem = charge0 - 1
# By default, the multiplicity of the cation/anion are mult0 + 1
# These are overridden with the cation_mult and anion_mult kwargs
multp = kwargs.get('cation_mult', mult0 + 1)
multm = kwargs.get('anion_mult', mult0 + 1)
# By default, we start the frac procedure on the 25th iteration
# when not reading a previous guess
frac_start = kwargs.get('frac_start', 25)
# By default, we occupy by tenths of electrons
HOMO_occs = kwargs.get('HOMO_occs', [1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.0])
LUMO_occs = kwargs.get('LUMO_occs', [1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.0])
# By default, H**O and LUMO are both in alpha
Z = 0;
for A in range(molecule.natom()):
Z += molecule.Z(A)
Z -= charge0
H**O = kwargs.get('H**O', (Z / 2 + 1 if (Z % 2) else Z / 2))
LUMO = kwargs.get('LUMO', H**O + 1)
# By default, DIIS in FRAC (1.0 occupation is always DIIS'd)
frac_diis = kwargs.get('frac_diis', True)
# By default, use the neutral orbitals as a guess for the anion
neutral_guess = kwargs.get('neutral_guess', True)
# By default, burn-in with UHF first, if UKS
hf_guess = False
if psi4.get_global_option('REFERENCE') == 'UKS':
hf_guess = kwargs.get('hf_guess', True)
# By default, re-guess at each N
continuous_guess = kwargs.get('continuous_guess', False)
# By default, drop the files to the molecule's name
root = kwargs.get('filename', molecule.name())
traverse_filename = root + '.traverse.dat'
# => Traverse <= #
occs = []
energies = []
potentials = []
convs = []
# => Run the neutral for its orbitals, if requested <= #
old_df_ints_io = psi4.get_global_option("DF_INTS_IO")
psi4.set_global_option("DF_INTS_IO", "SAVE")
old_guess = psi4.get_global_option("GUESS")
if (neutral_guess):
if (hf_guess):
psi4.set_global_option("REFERENCE","UHF")
energy('scf')
psi4.set_global_option("GUESS", "READ")
psi4.set_global_option("DF_INTS_IO", "LOAD")
# => Run the anion first <= #
molecule.set_molecular_charge(chargem)
molecule.set_multiplicity(multm)
# => Burn the anion in with hf, if requested <= #
if hf_guess:
psi4.set_global_option("REFERENCE","UHF")
energy('scf', molecule=molecule, **kwargs)
psi4.set_global_option("REFERENCE","UKS")
psi4.set_global_option("GUESS", "READ")
psi4.set_global_option("DF_INTS_IO", "SAVE")
psi4.set_global_option("FRAC_START", frac_start)
psi4.set_global_option("FRAC_RENORMALIZE", True)
psi4.set_global_option("FRAC_LOAD", False)
for occ in LUMO_occs:
psi4.set_global_option("FRAC_OCC", [LUMO])
psi4.set_global_option("FRAC_VAL", [occ])
E, wfn = energy('scf', return_wfn=True, molecule=molecule, **kwargs)
C = 1
if E == 0.0:
E = psi4.get_variable('SCF ITERATION ENERGY')
C = 0
if LUMO > 0:
eps = wfn.epsilon_a()
potentials.append(eps[int(LUMO) - 1])
else:
eps = wfn.epsilon_b()
potentials.append(eps[-int(LUMO) - 1])
occs.append(occ)
energies.append(E)
convs.append(C)
psi4.set_global_option("FRAC_START", 2)
psi4.set_global_option("FRAC_LOAD", True)
psi4.set_global_option("GUESS", "READ")
psi4.set_global_option("FRAC_DIIS", frac_diis)
psi4.set_global_option("DF_INTS_IO", "LOAD")
# => Run the neutral next <= #
molecule.set_molecular_charge(charge0)
molecule.set_multiplicity(mult0)
# Burn the neutral in with hf, if requested <= #
if not continuous_guess:
psi4.set_global_option("GUESS", old_guess)
if hf_guess:
psi4.set_global_option("FRAC_START", 0)
psi4.set_global_option("REFERENCE", "UHF")
energy('scf', molecule=molecule, **kwargs)
psi4.set_global_option("REFERENCE", "UKS")
psi4.set_global_option("GUESS", "READ")
psi4.set_global_option("FRAC_LOAD", False)
psi4.set_global_option("FRAC_START", frac_start)
psi4.set_global_option("FRAC_RENORMALIZE", True)
for occ in HOMO_occs:
psi4.set_global_option("FRAC_OCC", [H**O])
psi4.set_global_option("FRAC_VAL", [occ])
E, wfn = energy('scf', return_wfn=True, molecule=molecule, **kwargs)
C = 1
if E == 0.0:
E = psi4.get_variable('SCF ITERATION ENERGY')
C = 0
if LUMO > 0:
eps = wfn.epsilon_a()
potentials.append(eps[int(H**O) - 1])
else:
eps = wfn.epsilon_b()
potentials.append(eps[-int(H**O) - 1])
occs.append(occ - 1.0)
energies.append(E)
convs.append(C)
psi4.set_global_option("FRAC_START", 2)
psi4.set_global_option("FRAC_LOAD", True)
psi4.set_global_option("GUESS", "READ")
psi4.set_global_option("FRAC_DIIS", frac_diis)
psi4.set_global_option("DF_INTS_IO", "LOAD")
psi4.set_global_option("DF_INTS_IO", old_df_ints_io)
# => Print the results out <= #
E = {}
psi4.print_out("""\n ==> Fractional Occupation Traverse Results <==\n\n""")
psi4.print_out("""\t%-11s %-24s %-24s %11s\n""" % ('N', 'Energy', 'H**O Energy', 'Converged'))
for k in range(len(occs)):
psi4.print_out("""\t%11.3E %24.16E %24.16E %11d\n""" % (occs[k], energies[k], potentials[k], convs[k]))
E[occs[k]] = energies[k]
psi4.print_out('\n\t"You trying to be a hero Watkins?"\n')
psi4.print_out('\t"Just trying to kill some bugs sir!"\n')
psi4.print_out('\t\t\t-Starship Troopers\n')
# Drop the files out
fh = open(traverse_filename, 'w')
fh.write("""\t%-11s %-24s %-24s %11s\n""" % ('N', 'Energy', 'H**O Energy', 'Converged'))
for k in range(len(occs)):
fh.write("""\t%11.3E %24.16E %24.16E %11d\n""" % (occs[k], energies[k], potentials[k], convs[k]))
fh.close()
# Properly, should clone molecule but since not returned and easy to unblemish,
molecule.set_molecular_charge(charge0)
molecule.set_multiplicity(mult0)
return E
def run_gaussian_2(name, **kwargs):
# throw an exception for open-shells
if (psi4.get_option('SCF','REFERENCE') != 'RHF' ):
raise ValidationError("""g2 computations require "reference rhf".""")
# stash user options:
optstash = p4util.OptionsState(
['FNOCC','COMPUTE_TRIPLES'],
['FNOCC','COMPUTE_MP4_TRIPLES'],
['FREEZE_CORE'],
['MP2_TYPE'],
['SCF','SCF_TYPE'])
# override default scf_type
psi4.set_local_option('SCF','SCF_TYPE','PK')
# optimize geometry at scf level
psi4.clean()
psi4.set_global_option('BASIS',"6-31G(D)")
driver.optimize('scf')
psi4.clean()
# scf frequencies for zpe
# NOTE This line should not be needed, but without it there's a seg fault
scf_e, ref = driver.frequency('scf', return_wfn=True)
# thermodynamic properties
du = psi4.get_variable('INTERNAL ENERGY CORRECTION')
dh = psi4.get_variable('ENTHALPY CORRECTION')
dg = psi4.get_variable('GIBBS FREE ENERGY CORRECTION')
freqs = ref.frequencies()
nfreq = freqs.dim(0)
freqsum = 0.0
for i in range(0, nfreq):
freqsum += freqs.get(i)
zpe = freqsum / p4const.psi_hartree2wavenumbers * 0.8929 * 0.5
psi4.clean()
# optimize geometry at mp2 (no frozen core) level
# note: freeze_core isn't an option in MP2
psi4.set_global_option('FREEZE_CORE',"FALSE")
psi4.set_global_option('MP2_TYPE', 'CONV')
driver.optimize('mp2')
psi4.clean()
# qcisd(t)
psi4.set_local_option('FNOCC','COMPUTE_MP4_TRIPLES',"TRUE")
psi4.set_global_option('FREEZE_CORE',"TRUE")
psi4.set_global_option('BASIS',"6-311G(D_P)")
ref = driver.proc.run_fnocc('qcisd(t)', return_wfn=True, **kwargs)
# HLC: high-level correction based on number of valence electrons
nirrep = ref.nirrep()
frzcpi = ref.frzcpi()
nfzc = 0
for i in range (0,nirrep):
nfzc += frzcpi[i]
nalpha = ref.nalpha() - nfzc
nbeta = ref.nbeta() - nfzc
# hlc of gaussian-2
hlc = -0.00481 * nalpha -0.00019 * nbeta
# hlc of gaussian-1
hlc1 = -0.00614 * nalpha
eqci_6311gdp = psi4.get_variable("QCISD(T) TOTAL ENERGY")
emp4_6311gd = psi4.get_variable("MP4 TOTAL ENERGY")
emp2_6311gd = psi4.get_variable("MP2 TOTAL ENERGY")
psi4.clean()
# correction for diffuse functions
psi4.set_global_option('BASIS',"6-311+G(D_P)")
driver.energy('mp4')
emp4_6311pg_dp = psi4.get_variable("MP4 TOTAL ENERGY")
emp2_6311pg_dp = psi4.get_variable("MP2 TOTAL ENERGY")
psi4.clean()
# correction for polarization functions
psi4.set_global_option('BASIS',"6-311G(2DF_P)")
driver.energy('mp4')
emp4_6311g2dfp = psi4.get_variable("MP4 TOTAL ENERGY")
emp2_6311g2dfp = psi4.get_variable("MP2 TOTAL ENERGY")
psi4.clean()
# big basis mp2
psi4.set_global_option('BASIS',"6-311+G(3DF_2P)")
#run_fnocc('_mp2',**kwargs)
driver.energy('mp2')
emp2_big = psi4.get_variable("MP2 TOTAL ENERGY")
psi4.clean()
eqci = eqci_6311gdp
e_delta_g2 = emp2_big + emp2_6311gd - emp2_6311g2dfp - emp2_6311pg_dp
e_plus = emp4_6311pg_dp - emp4_6311gd
e_2df = emp4_6311g2dfp - emp4_6311gd
eg2 = eqci + e_delta_g2 + e_plus + e_2df
eg2_mp2_0k = eqci + (emp2_big - emp2_6311gd) + hlc + zpe
psi4.print_out('\n')
psi4.print_out(' ==> G1/G2 Energy Components <==\n')
psi4.print_out('\n')
psi4.print_out(' QCISD(T): %20.12lf\n' % eqci)
psi4.print_out(' E(Delta): %20.12lf\n' % e_delta_g2)
psi4.print_out(' E(2DF): %20.12lf\n' % e_2df)
psi4.print_out(' E(+): %20.12lf\n' % e_plus)
psi4.print_out(' E(G1 HLC): %20.12lf\n' % hlc1)
psi4.print_out(' E(G2 HLC): %20.12lf\n' % hlc)
psi4.print_out(' E(ZPE): %20.12lf\n' % zpe)
psi4.print_out('\n')
psi4.print_out(' ==> 0 Kelvin Results <==\n')
psi4.print_out('\n')
eg2_0k = eg2 + zpe + hlc
psi4.print_out(' G1: %20.12lf\n' % (eqci + e_plus + e_2df + hlc1 + zpe))
psi4.print_out(' G2(MP2): %20.12lf\n' % eg2_mp2_0k)
psi4.print_out(' G2: %20.12lf\n' % eg2_0k)
psi4.set_variable("G1 TOTAL ENERGY",eqci + e_plus + e_2df + hlc1 + zpe)
psi4.set_variable("G2 TOTAL ENERGY",eg2_0k)
psi4.set_variable("G2(MP2) TOTAL ENERGY",eg2_mp2_0k)
psi4.print_out('\n')
T = psi4.get_global_option('T')
psi4.print_out(' ==> %3.0lf Kelvin Results <==\n'% T)
psi4.print_out('\n')
internal_energy = eg2_mp2_0k + du - zpe / 0.8929
enthalpy = eg2_mp2_0k + dh - zpe / 0.8929
gibbs = eg2_mp2_0k + dg - zpe / 0.8929
psi4.print_out(' G2(MP2) energy: %20.12lf\n' % internal_energy )
psi4.print_out(' G2(MP2) enthalpy: %20.12lf\n' % enthalpy)
psi4.print_out(' G2(MP2) free energy: %20.12lf\n' % gibbs)
psi4.print_out('\n')
psi4.set_variable("G2(MP2) INTERNAL ENERGY",internal_energy)
psi4.set_variable("G2(MP2) ENTHALPY",enthalpy)
psi4.set_variable("G2(MP2) FREE ENERGY",gibbs)
internal_energy = eg2_0k + du - zpe / 0.8929
enthalpy = eg2_0k + dh - zpe / 0.8929
gibbs = eg2_0k + dg - zpe / 0.8929
psi4.print_out(' G2 energy: %20.12lf\n' % internal_energy )
psi4.print_out(' G2 enthalpy: %20.12lf\n' % enthalpy)
psi4.print_out(' G2 free energy: %20.12lf\n' % gibbs)
psi4.set_variable("CURRENT ENERGY",eg2_0k)
psi4.set_variable("G2 INTERNAL ENERGY",internal_energy)
psi4.set_variable("G2 ENTHALPY",enthalpy)
psi4.set_variable("G2 FREE ENERGY",gibbs)
psi4.clean()
optstash.restore()
# return 0K g2 results
return eg2_0k
def ip_fitting(molecule, omega_l, omega_r, **kwargs):
kwargs = p4util.kwargs_lower(kwargs)
# By default, zero the omega to 3 digits
omega_tol = kwargs.get('omega_tolerance', 1.0E-3)
# By default, do up to twenty iterations
maxiter = kwargs.get('maxiter', 20)
# By default, do not read previous 180 orbitals file
read = False
read180 = ''
if 'read' in kwargs:
read = True
read180 = kwargs['read']
# The molecule is required, and should be the neutral species
molecule.update_geometry()
charge0 = molecule.molecular_charge()
mult0 = molecule.multiplicity()
# How many electrons are there?
N = 0
for A in range(molecule.natom()):
N += molecule.Z(A)
N -= charge0
N = int(N)
Nb = int((N - mult0 + 1) / 2)
Na = int(N - Nb)
# Work in the ot namespace for this procedure
psi4.IO.set_default_namespace("ot")
# Burn in to determine orbital eigenvalues
if read:
psi4.set_global_option("GUESS", "READ")
copy_file_to_scratch(read180, 'psi', 'ot', 180)
old_guess = psi4.get_global_option("GUESS")
psi4.set_global_option("DF_INTS_IO", "SAVE")
psi4.print_out("""\n\t==> IP Fitting SCF: Burn-in <==\n""")
E, wfn = energy('scf', return_wfn=True, molecule=molecule, **kwargs)
psi4.set_global_option("DF_INTS_IO", "LOAD")
# Determine H**O, to determine mult1
eps_a = wfn.epsilon_a()
eps_b = wfn.epsilon_b()
if Na == Nb:
H**O = -Nb
elif Nb == 0:
H**O = Na
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if E_a >= E_b:
H**O = Na
else:
H**O = -Nb
Na1 = Na;
Nb1 = Nb;
if H**O > 0:
Na1 = Na1 - 1;
else:
Nb1 = Nb1 - 1;
charge1 = charge0 + 1;
mult1 = Na1 - Nb1 + 1
omegas = []
E0s = []
E1s = []
kIPs = []
IPs = []
types = []
# Right endpoint
psi4.set_global_option('DFT_OMEGA', omega_r)
# Neutral
if read:
psi4.set_global_option("GUESS", "READ")
p4util.copy_file_to_scratch(read180, 'psi', 'ot', 180)
molecule.set_molecular_charge(charge0)
molecule.set_multiplicity(mult0)
psi4.print_out("""\n\t==> IP Fitting SCF: Neutral, Right Endpoint <==\n""")
E0r, wfn = energy('scf', return_wfn=True, molecule=molecule, **kwargs)
eps_a = wfn.epsilon_a()
eps_b = wfn.epsilon_b()
E_HOMO = 0.0;
if Nb == 0:
E_HOMO = eps_a[int(Na - 1)]
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if E_a >= E_b:
E_HOMO = E_a
else:
E_HOMO = E_b
E_HOMOr = E_HOMO
psi4.IO.change_file_namespace(180, "ot", "neutral")
# Cation
if read:
psi4.set_global_option("GUESS", "READ")
p4util.copy_file_to_scratch(read180, 'psi', 'ot', 180)
molecule.set_molecular_charge(charge1)
molecule.set_multiplicity(mult1)
psi4.print_out("""\n\t==> IP Fitting SCF: Cation, Right Endpoint <==\n""")
E1r = energy('scf', molecule=molecule, **kwargs)
psi4.IO.change_file_namespace(180, "ot", "cation")
IPr = E1r - E0r;
kIPr = -E_HOMOr;
delta_r = IPr - kIPr;
if IPr > kIPr:
message = ("""\n***IP Fitting Error: Right Omega limit should have kIP > IP""")
raise ValidationError(message)
omegas.append(omega_r)
types.append('Right Limit')
E0s.append(E0r)
E1s.append(E1r)
IPs.append(IPr)
kIPs.append(kIPr)
# Use previous orbitals from here out
psi4.set_global_option("GUESS", "READ")
# Left endpoint
psi4.set_global_option('DFT_OMEGA', omega_l)
# Neutral
psi4.IO.change_file_namespace(180, "neutral", "ot")
molecule.set_molecular_charge(charge0)
molecule.set_multiplicity(mult0)
psi4.print_out("""\n\t==> IP Fitting SCF: Neutral, Left Endpoint <==\n""")
E0l, wfn = energy('scf', return_wfn=True, molecule=molecule, **kwargs)
eps_a = wfn.epsilon_a()
eps_b = wfn.epsilon_b()
E_HOMO = 0.0
if Nb == 0:
E_HOMO = eps_a[int(Na - 1)]
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if E_a >= E_b:
E_HOMO = E_a
else:
E_HOMO = E_b
E_HOMOl = E_HOMO
psi4.IO.change_file_namespace(180, "ot", "neutral")
# Cation
psi4.IO.change_file_namespace(180, "cation", "ot")
molecule.set_molecular_charge(charge1)
molecule.set_multiplicity(mult1)
psi4.print_out("""\n\t==> IP Fitting SCF: Cation, Left Endpoint <==\n""")
E1l = energy('scf', molecule=molecule, **kwargs)
psi4.IO.change_file_namespace(180, "ot", "cation")
IPl = E1l - E0l
kIPl = -E_HOMOl
delta_l = IPl - kIPl
if IPl < kIPl:
message = ("""\n***IP Fitting Error: Left Omega limit should have kIP < IP""")
raise ValidationError(message)
omegas.append(omega_l)
types.append('Left Limit')
E0s.append(E0l)
E1s.append(E1l)
IPs.append(IPl)
kIPs.append(kIPl)
converged = False
repeat_l = 0
repeat_r = 0
step = 0
while True:
step = step + 1
# Regula Falsi (modified)
if repeat_l > 1:
delta_l = delta_l / 2.0
if repeat_r > 1:
delta_r = delta_r / 2.0
omega = - (omega_r - omega_l) / (delta_r - delta_l) * delta_l + omega_l
psi4.set_global_option('DFT_OMEGA', omega)
# Neutral
psi4.IO.change_file_namespace(180, "neutral", "ot")
molecule.set_molecular_charge(charge0)
molecule.set_multiplicity(mult0)
psi4.print_out("""\n\t==> IP Fitting SCF: Neutral, Omega = %11.3E <==\n""" % omega)
E0, wfn = energy('scf', return_wfn=True, molecule=molecule, **kwargs)
eps_a = wfn.epsilon_a()
eps_b = wfn.epsilon_b()
E_HOMO = 0.0
if Nb == 0:
E_HOMO = eps_a[int(Na - 1)]
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if E_a >= E_b:
E_HOMO = E_a
else:
E_HOMO = E_b
psi4.IO.change_file_namespace(180, "ot", "neutral")
# Cation
psi4.IO.change_file_namespace(180, "cation", "ot")
molecule.set_molecular_charge(charge1)
molecule.set_multiplicity(mult1)
psi4.print_out("""\n\t==> IP Fitting SCF: Cation, Omega = %11.3E <==\n""" % omega)
E1 = energy('scf', molecule=molecule, **kwargs)
psi4.IO.change_file_namespace(180, "ot", "cation")
IP = E1 - E0
kIP = -E_HOMO
delta = IP - kIP
if kIP > IP:
omega_r = omega
E0r = E0
E1r = E1
IPr = IP
kIPr = kIP
delta_r = delta
repeat_r = 0
repeat_l = repeat_l + 1
else:
omega_l = omega
E0l = E0
E1l = E1
IPl = IP
kIPl = kIP
delta_l = delta
repeat_l = 0;
repeat_r = repeat_r + 1
omegas.append(omega)
types.append('Regula-Falsi')
E0s.append(E0)
E1s.append(E1)
IPs.append(IP)
kIPs.append(kIP)
# Termination
if (abs(omega_l - omega_r) < omega_tol or step > maxiter):
converged = True
break
# Properly, should clone molecule but since not returned and easy to unblemish,
molecule.set_molecular_charge(charge0)
molecule.set_multiplicity(mult0)
psi4.IO.set_default_namespace("")
psi4.print_out("""\n\t==> IP Fitting Results <==\n\n""")
psi4.print_out("""\t => Occupation Determination <= \n\n""")
psi4.print_out("""\t %6s %6s %6s %6s %6s %6s\n""" % ('N', 'Na', 'Nb', 'Charge', 'Mult', 'H**O'))
psi4.print_out("""\t Neutral: %6d %6d %6d %6d %6d %6d\n""" % (N, Na, Nb, charge0, mult0, H**O))
psi4.print_out("""\t Cation: %6d %6d %6d %6d %6d\n\n""" % (N - 1, Na1, Nb1, charge1, mult1))
psi4.print_out("""\t => Regula Falsi Iterations <=\n\n""")
psi4.print_out("""\t%3s %11s %14s %14s %14s %s\n""" % ('N','Omega','IP','kIP','Delta','Type'))
for k in range(len(omegas)):
psi4.print_out("""\t%3d %11.3E %14.6E %14.6E %14.6E %s\n""" %
(k + 1, omegas[k], IPs[k], kIPs[k], IPs[k] - kIPs[k], types[k]))
if converged:
psi4.print_out("""\n\tIP Fitting Converged\n""")
psi4.print_out("""\tFinal omega = %14.6E\n""" % ((omega_l + omega_r) / 2))
psi4.print_out("""\n\t"M,I. does the dying. Fleet just does the flying."\n""")
psi4.print_out("""\t\t\t-Starship Troopers\n""")
else:
psi4.print_out("""\n\tIP Fitting did not converge!\n""")
psi4.set_global_option("DF_INTS_IO", "NONE")
psi4.set_global_option("GUESS", old_guess)
def frac_nuke(molecule, **kwargs):
kwargs = p4util.kwargs_lower(kwargs)
# The molecule is required, and should be the neutral species
molecule.update_geometry()
charge0 = molecule.molecular_charge()
mult0 = molecule.multiplicity()
# By default, we start the frac procedure on the 25th iteration
# when not reading a previous guess
frac_start = kwargs.get('frac_start', 25)
# By default, we occupy by tenths of electrons
foccs = kwargs.get('foccs',
[1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.0])
# By default, H**O and LUMO are both in alpha
N = 0
for A in range(molecule.natom()):
N += molecule.Z(A)
N -= charge0
N = int(N)
Nb = int((N - mult0 + 1) / 2)
Na = int(N - Nb)
charge = charge0
mult = mult0
# By default, nuke all the electrons
Nmin = 0
if ('nmax' in kwargs):
Nmin = N - int(kwargs['nmax'])
# By default, DIIS in FRAC (1.0 occupation is always DIIS'd)
frac_diis = kwargs.get('frac_diis', True)
# By default, drop the files to the molecule's name
root = kwargs.get('filename', molecule.name())
traverse_filename = root + '.traverse.dat'
stats_filename = root + '.stats.dat'
# => Traverse <= #
psi4.set_global_option("DF_INTS_IO", "SAVE")
Ns = []
energies = []
potentials = []
convs = []
stats = []
# Run one SCF to burn things in
E, wfn = energy('scf', return_wfn=True, molecule=molecule, **kwargs)
# Determine H**O
eps_a = wfn.epsilon_a()
eps_b = wfn.epsilon_b()
if Na == Nb:
H**O = -Nb
elif Nb == 0:
H**O = Na
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if E_a >= E_b:
H**O = Na
else:
H**O = -Nb
stats.append("""\t%6d %6d %6d %6d %6d %6d\n""" %
(N, Na, Nb, charge, mult, H**O))
if H**O > 0:
Na = Na - 1
else:
Nb = Nb - 1
charge = charge + 1
mult = Na - Nb + 1
psi4.set_global_option("DF_INTS_IO", "LOAD")
psi4.set_global_option("FRAC_START", frac_start)
psi4.set_global_option("FRAC_RENORMALIZE", True)
# Nuke 'em Rico!
for Nintegral in range(N, Nmin, -1):
# Nuke the current H**O
for occ in foccs:
psi4.set_global_option("FRAC_OCC", [H**O])
psi4.set_global_option("FRAC_VAL", [occ])
E, wfn = energy('scf',
return_wfn=True,
molecule=molecule,
**kwargs)
C = 1
if E == 0.0:
E = psi4.get_variable('SCF ITERATION ENERGY')
C = 0
if H**O > 0:
eps = wfn.epsilon_a()
potentials.append(eps[H**O - 1])
else:
eps = wfn.epsilon_b()
potentials.append(eps[-H**O - 1])
Ns.append(Nintegral + occ - 1.0)
energies.append(E)
convs.append(C)
psi4.set_global_option("FRAC_START", 2)
psi4.set_global_option("FRAC_LOAD", True)
psi4.set_global_option("FRAC_DIIS", frac_diis)
psi4.set_global_option("GUESS", "READ")
# Set the next charge/mult
molecule.set_molecular_charge(charge)
molecule.set_multiplicity(mult)
# Determine H**O
print('DGAS: What ref should this point to?')
#ref = psi4.legacy_wavefunction()
eps_a = wfn.epsilon_a()
eps_b = wfn.epsilon_b()
if Na == Nb:
H**O = -Nb
elif Nb == 0:
H**O = Na
else:
E_a = eps_a[int(Na - 1)]
E_b = eps_b[int(Nb - 1)]
if E_a >= E_b:
H**O = Na
else:
H**O = -Nb
stats.append("""\t%6d %6d %6d %6d %6d %6d\n""" %
(Nintegral - 1, Na, Nb, charge, mult, H**O))
if H**O > 0:
Na = Na - 1
else:
Nb = Nb - 1
charge = charge + 1
mult = Na - Nb + 1
psi4.set_global_option("DF_INTS_IO", "NONE")
# => Print the results out <= #
E = {}
psi4.print_out("""\n ==> Fractional Occupation Nuke Results <==\n\n""")
psi4.print_out("""\t%-11s %-24s %-24s %11s\n""" %
('N', 'Energy', 'H**O Energy', 'Converged'))
for k in range(len(Ns)):
psi4.print_out("""\t%11.3E %24.16E %24.16E %11d\n""" %
(Ns[k], energies[k], potentials[k], convs[k]))
E[Ns[k]] = energies[k]
psi4.print_out('\n')
psi4.print_out("""\t%6s %6s %6s %6s %6s %6s\n""" %
('N', 'Na', 'Nb', 'Charge', 'Mult', 'H**O'))
for line in stats:
psi4.print_out(line)
psi4.print_out(
'\n\t"You shoot a nuke down a bug hole, you got a lot of dead bugs"\n')
psi4.print_out('\t\t\t-Starship Troopers\n')
# Drop the files out
fh = open(traverse_filename, 'w')
fh.write("""\t%-11s %-24s %-24s %11s\n""" %
('N', 'Energy', 'H**O Energy', 'Converged'))
for k in range(len(Ns)):
fh.write("""\t%11.3E %24.16E %24.16E %11d\n""" %
(Ns[k], energies[k], potentials[k], convs[k]))
fh.close()
fh = open(stats_filename, 'w')
fh.write("""\t%6s %6s %6s %6s %6s %6s\n""" %
('N', 'Na', 'Nb', 'Charge', 'Mult', 'H**O'))
for line in stats:
fh.write(line)
fh.close()
# Properly, should clone molecule but since not returned and easy to unblemish,
molecule.set_molecular_charge(charge0)
molecule.set_multiplicity(mult0)
return E
def run_gaussian_2(name, **kwargs):
# throw an exception for open-shells
if (psi4.get_option('SCF', 'REFERENCE') != 'RHF'):
raise ValidationError("""g2 computations require "reference rhf".""")
# stash user options:
optstash = p4util.OptionsState(['FNOCC', 'COMPUTE_TRIPLES'],
['FNOCC', 'COMPUTE_MP4_TRIPLES'],
['FREEZE_CORE'], ['MP2_TYPE'],
['SCF', 'SCF_TYPE'])
# override default scf_type
psi4.set_local_option('SCF', 'SCF_TYPE', 'PK')
# optimize geometry at scf level
psi4.clean()
psi4.set_global_option('BASIS', "6-31G(D)")
driver.optimize('scf')
psi4.clean()
# scf frequencies for zpe
# NOTE This line should not be needed, but without it there's a seg fault
scf_e, ref = driver.frequency('scf', return_wfn=True)
# thermodynamic properties
du = psi4.get_variable('INTERNAL ENERGY CORRECTION')
dh = psi4.get_variable('ENTHALPY CORRECTION')
dg = psi4.get_variable('GIBBS FREE ENERGY CORRECTION')
freqs = ref.frequencies()
nfreq = freqs.dim(0)
freqsum = 0.0
for i in range(0, nfreq):
freqsum += freqs.get(i)
zpe = freqsum / p4const.psi_hartree2wavenumbers * 0.8929 * 0.5
psi4.clean()
# optimize geometry at mp2 (no frozen core) level
# note: freeze_core isn't an option in MP2
psi4.set_global_option('FREEZE_CORE', "FALSE")
psi4.set_global_option('MP2_TYPE', 'CONV')
driver.optimize('mp2')
psi4.clean()
# qcisd(t)
psi4.set_local_option('FNOCC', 'COMPUTE_MP4_TRIPLES', "TRUE")
psi4.set_global_option('FREEZE_CORE', "TRUE")
psi4.set_global_option('BASIS', "6-311G(D_P)")
ref = driver.proc.run_fnocc('qcisd(t)', return_wfn=True, **kwargs)
# HLC: high-level correction based on number of valence electrons
nirrep = ref.nirrep()
frzcpi = ref.frzcpi()
nfzc = 0
for i in range(0, nirrep):
nfzc += frzcpi[i]
nalpha = ref.nalpha() - nfzc
nbeta = ref.nbeta() - nfzc
# hlc of gaussian-2
hlc = -0.00481 * nalpha - 0.00019 * nbeta
# hlc of gaussian-1
hlc1 = -0.00614 * nalpha
eqci_6311gdp = psi4.get_variable("QCISD(T) TOTAL ENERGY")
emp4_6311gd = psi4.get_variable("MP4 TOTAL ENERGY")
emp2_6311gd = psi4.get_variable("MP2 TOTAL ENERGY")
psi4.clean()
# correction for diffuse functions
psi4.set_global_option('BASIS', "6-311+G(D_P)")
driver.energy('mp4')
emp4_6311pg_dp = psi4.get_variable("MP4 TOTAL ENERGY")
emp2_6311pg_dp = psi4.get_variable("MP2 TOTAL ENERGY")
psi4.clean()
# correction for polarization functions
psi4.set_global_option('BASIS', "6-311G(2DF_P)")
driver.energy('mp4')
emp4_6311g2dfp = psi4.get_variable("MP4 TOTAL ENERGY")
emp2_6311g2dfp = psi4.get_variable("MP2 TOTAL ENERGY")
psi4.clean()
# big basis mp2
psi4.set_global_option('BASIS', "6-311+G(3DF_2P)")
#run_fnocc('_mp2',**kwargs)
driver.energy('mp2')
emp2_big = psi4.get_variable("MP2 TOTAL ENERGY")
psi4.clean()
eqci = eqci_6311gdp
e_delta_g2 = emp2_big + emp2_6311gd - emp2_6311g2dfp - emp2_6311pg_dp
e_plus = emp4_6311pg_dp - emp4_6311gd
e_2df = emp4_6311g2dfp - emp4_6311gd
eg2 = eqci + e_delta_g2 + e_plus + e_2df
eg2_mp2_0k = eqci + (emp2_big - emp2_6311gd) + hlc + zpe
psi4.print_out('\n')
psi4.print_out(' ==> G1/G2 Energy Components <==\n')
psi4.print_out('\n')
psi4.print_out(' QCISD(T): %20.12lf\n' % eqci)
psi4.print_out(' E(Delta): %20.12lf\n' % e_delta_g2)
psi4.print_out(' E(2DF): %20.12lf\n' % e_2df)
psi4.print_out(' E(+): %20.12lf\n' % e_plus)
psi4.print_out(' E(G1 HLC): %20.12lf\n' % hlc1)
psi4.print_out(' E(G2 HLC): %20.12lf\n' % hlc)
psi4.print_out(' E(ZPE): %20.12lf\n' % zpe)
psi4.print_out('\n')
psi4.print_out(' ==> 0 Kelvin Results <==\n')
psi4.print_out('\n')
eg2_0k = eg2 + zpe + hlc
psi4.print_out(' G1: %20.12lf\n' %
(eqci + e_plus + e_2df + hlc1 + zpe))
psi4.print_out(' G2(MP2): %20.12lf\n' % eg2_mp2_0k)
psi4.print_out(' G2: %20.12lf\n' % eg2_0k)
psi4.set_variable("G1 TOTAL ENERGY", eqci + e_plus + e_2df + hlc1 + zpe)
psi4.set_variable("G2 TOTAL ENERGY", eg2_0k)
psi4.set_variable("G2(MP2) TOTAL ENERGY", eg2_mp2_0k)
psi4.print_out('\n')
T = psi4.get_global_option('T')
psi4.print_out(' ==> %3.0lf Kelvin Results <==\n' % T)
psi4.print_out('\n')
internal_energy = eg2_mp2_0k + du - zpe / 0.8929
enthalpy = eg2_mp2_0k + dh - zpe / 0.8929
gibbs = eg2_mp2_0k + dg - zpe / 0.8929
psi4.print_out(' G2(MP2) energy: %20.12lf\n' % internal_energy)
psi4.print_out(' G2(MP2) enthalpy: %20.12lf\n' % enthalpy)
psi4.print_out(' G2(MP2) free energy: %20.12lf\n' % gibbs)
psi4.print_out('\n')
psi4.set_variable("G2(MP2) INTERNAL ENERGY", internal_energy)
psi4.set_variable("G2(MP2) ENTHALPY", enthalpy)
psi4.set_variable("G2(MP2) FREE ENERGY", gibbs)
internal_energy = eg2_0k + du - zpe / 0.8929
enthalpy = eg2_0k + dh - zpe / 0.8929
gibbs = eg2_0k + dg - zpe / 0.8929
psi4.print_out(' G2 energy: %20.12lf\n' % internal_energy)
psi4.print_out(' G2 enthalpy: %20.12lf\n' % enthalpy)
psi4.print_out(' G2 free energy: %20.12lf\n' % gibbs)
psi4.set_variable("CURRENT ENERGY", eg2_0k)
psi4.set_variable("G2 INTERNAL ENERGY", internal_energy)
psi4.set_variable("G2 ENTHALPY", enthalpy)
psi4.set_variable("G2 FREE ENERGY", gibbs)
psi4.clean()
optstash.restore()
# return 0K g2 results
return eg2_0k