def test_hooh_fixed_HOOH_tor():
# Constrained minimization with H-O-O-H dihedral fixed to 120.0 degrees.
hooh = psi4.geometry("""
H
O 1 0.90
O 2 1.40 1 100.0
H 3 0.90 2 100.0 1 115.0
""")
psi4.set_options({
'diis': 'false',
'basis': 'cc-pvdz',
'g_convergence': 'gau_verytight'
})
dihedral_angle = ("""
1 2 3 4 120.0
""")
psi4.set_module_options('Optking', {'fixed_dihedral': dihedral_angle})
Psi4Opt.calcName = 'hf'
thisenergy = Psi4Opt.Psi4Opt()
assert psi4.compare_values(
HOOH_120_dihedral, thisenergy, 6,
"Int. Coord. RHF opt of HOOH with H-O-O-H fixed to 120, energy") #TEST
def test_scf():
bas_list = ['STO-3G','DZ','DZP']
mol_list = ['H2O', 'CO2', 'C2H4']
for name in mol_list:
geom = mesp.mollib[name]
geom += '\nsymmetry c1'
for bas in bas_list:
psi4.core.clean()
mol = mesp.Molecule(name,geom,bas)
psi4.set_options({
'basis':bas,
'scf_type':'pk',
'freeze_core':'false',
'e_convergence':1e-12,
'd_convergence':1e-12})
psi4.set_module_options('SCF',
{'e_convergence': 1e-12, 'd_convergence': 1e-12,
'DIIS': True, 'scf_type':'pk'})
print("Results for {}/SCF/{}".format(name,bas))
mesp.scf.do_scf(mol)
E_mesp = mol.E_SCF
E_psi4 = psi4.energy('SCF',molecule=mol.p4mol)
print("mesp energy: {}".format(E_mesp))
print("Psi4 energy: {}\n\n".format(E_psi4))
psi4.compare_values(E_psi4,E_mesp,11,"RHF Energy")
def test_mp2():
bas_list = ['STO-3G','DZ']
mol_list = ['H2O']
for name in mol_list:
geom = mesp.mollib[name]
geom += '\nsymmetry c1'
for bas in bas_list:
psi4.core.clean()
mol = mesp.Molecule(name,geom,bas)
psi4.set_options({
'basis':bas,
'scf_type':'pk',
'mp2_type':'conv',
'freeze_core':'false',
'e_convergence':1e-12,
'd_convergence':1e-12})
psi4.set_module_options('SCF',
{'e_convergence': 1e-12, 'd_convergence': 1e-12,
'DIIS': True, 'scf_type':'pk'})
print("Results for {}/MP2/{}".format(name,bas))
mesp.mp2.do_mp2(mol)
E_mesp = mol.E_MP2
E_psi4 = psi4.energy('MP2')
print("mesp energy: {}".format(E_mesp))
print("Psi4 energy: {}".format(E_psi4))
psi4.compare_values(E_psi4,E_mesp,11,"MP2 Energy")
def test_hooh_freeze_xyz_Hs():
# Freeze H xyz in HOOH.
hooh = psi4.geometry("""
H 0.90 0.80 0.5
O 0.00 0.70 0.0
O 0.00 -0.70 0.0
H -0.90 -0.80 0.5
no_com
no_reorient
""")
psi4.set_options({
'basis': 'cc-pvdz',
'opt_coordinates': 'cartesian',
'g_convergence': 'gau_tight',
'geom_maxiter': 20,
'consecutive_backsteps': 1 # TEST backsteps
})
freeze_list = """ 1 Xyz 4 xYz """
psi4.set_module_options('Optking', {'frozen_cartesian': freeze_list})
#set optking frozen_cartesian $freeze_list
Psi4Opt.calcName = 'hf'
thisenergy = Psi4Opt.Psi4Opt()
assert psi4.compare_values(HOOH_E_fixed_H_xyz, thisenergy, 6,
"Cart. Coord. RHF opt of HOOH with H's xyz frozen, energy") #TEST
def test_frozen_coords(option, expected):
# Constrained minimization with frozen bond, bend, and torsion
hooh = psi4.geometry("""
H
O 1 0.90
O 2 1.40 1 100.0
H 3 0.90 2 100.0 1 115.0
""")
psi4.core.clean_options()
psi4_options = {
'diis': 'false',
'basis': 'cc-PVDZ',
'scf_type': 'pk',
'print': 4,
'g_convergence': 'gau_tight'
}
psi4.set_options(psi4_options)
psi4.set_module_options('OPTKING', option)
json_output = optking.optimize_psi4('hf')
thisenergy = json_output['energies'][-1]
assert psi4.compare_values(expected, thisenergy, 6) # TEST
def test_hooh_fixed_OH_stre():
hooh = psi4.geometry("""
H
O 1 0.90
O 2 1.40 1 100.0
H 3 0.90 2 100.0 1 115.0
""")
psi4.set_options({
'diis': 'false',
'basis': 'cc-pvdz',
'g_convergence': 'gau_verytight'
})
OH_bondlengths = ("""
1 2 0.950
3 4 0.950
""")
psi4.set_module_options('Optking', {'fixed_distance': OH_bondlengths})
Psi4Opt.calcName = 'hf'
thisenergy = Psi4Opt.Psi4Opt()
assert psi4.compare_values(
OH_950_stre, thisenergy, 6,
"Int. Coord. RHF opt of HOOH with O-H fixed to 0.95, energy") #TEST
def test_fci_ecp_2():
"""Water-Argon complex with ECP present; CASCI(6,6)."""
nucenergy = 23.253113522963400
refenergy = -96.68319147222
arwater = psi4.geometry("""
Ar 0.000000000000 0.000000000000 3.000000000000
O 0.000000000000 0.000000000000 -0.071143036192
H 0.000000000000 -0.758215806856 0.564545805801
H 0.000000000000 0.758215806856 0.564545805801
""")
psi4.set_options({
'scf_type': 'pk',
'basis': 'lanl2dz',
'df_scf_guess': False,
'd_convergence': 10,
})
psi4.set_module_options("FORTE", {
'job_type': 'fci',
'restricted_docc': [4,0,1,1],
'active': [2,0,2,2],
})
e = psi4.energy('forte')
assert psi4.compare_values(nucenergy, arwater.nuclear_repulsion_energy(), 10, "Nuclear repulsion energy")
assert psi4.compare_values(refenergy, e, 10, "FCI energy with ECP")
def test_input_multistate():
"""Test input for a multi-state computation using the `AVG_STATE` keyword."""
psi4.geometry("""
Li
H 1 3.0
units bohr
""")
ref_energies = {
'1A1': [-8.008550659909, -7.890309067618, -7.776162395969],
'1A2': [-7.396156201690, -7.321587400358, -7.262899599968],
'1B1': [-7.853436217153, -7.749808606728, -7.382069881110],
'1B2': [-7.853436217170, -7.749808606704, -7.382069881071],
}
# need to clean the options otherwise this job will interfere
forte.clean_options()
psi4.set_options({'basis': 'DZ', 'scf_type': 'pk', 'e_convergence': 12})
psi4.set_module_options(
'FORTE', {
'active_space_solver': 'fci',
'active': [8, 0, 2, 2],
'restricted_docc': [0, 0, 0, 0],
'avg_state': [[0, 1, 3], [1, 1, 3], [2, 1, 3], [3, 1, 3]],
'ms': 0.0
})
efci = psi4.energy('forte')
for k, vals in ref_energies.items():
for i in range(3):
assert psi4.core.variable(f'ENERGY ROOT {i} {k}') == pytest.approx(
vals[i], 1.0e-9)
def test_hooh_freeze_xyz_Hs(options, expected):
hooh = psi4.geometry("""
H 0.90 0.80 0.5
O 0.00 0.70 0.0
O 0.00 -0.70 0.0
H -0.90 -0.80 0.5
""")
psi4.core.clean_options()
psi4_options = {
"basis": "cc-pvdz",
"opt_coordinates": "cartesian",
"g_convergence": "gau_tight",
"geom_maxiter": 20,
"consecutive_backsteps": 1,
}
psi4.set_options(psi4_options)
psi4.set_module_options("OPTKING", options)
json_output = optking.optimize_psi4("hf")
thisenergy = json_output["energies"][-1] # TEST
assert psi4.compare_values(expected, thisenergy, 6) # TEST
def v2rdm_psi4():
mol = psi4.geometry("""
0 1
b
h 1 1.1
""")
psi4.set_options({
'basis': 'sto-3g',
'scf_type': 'out_of_core',
'd_convergence': 1e-10,
'maxiter': 500,
})
psi4.set_module_options('hilbert', {
#'sdp_solver': 'rrsdp',
'positivity': 'dqg',
'r_convergence': 1e-5,
'e_convergence': 1e-4,
'maxiter': 20000,
})
psi4.activate(mol)
# get scf wfn
scf_energy,ref_wfn = psi4.energy('scf',return_wfn=True)
# grab options object
options = psi4.core.get_options()
options.set_current_module('HILBERT')
v2rdm_psi4 = hilbert.v2RDMHelper(ref_wfn,options)
current_energy = v2rdm_psi4.compute_energy()
return current_energy, mol.nuclear_repulsion_energy()
def __init__(self,memory=2):
psi4.set_module_options('SCF', {'SCF_TYPE':'PK'})
psi4.set_module_options('SCF', {'E_CONVERGENCE':1e-14})
psi4.set_module_options('SCF', {'D_CONVERGENCE':1e-14})
psi4.set_module_options('CCENERGY', {'E_CONVERGENCE':1e-16})
psi4.set_module_options('CCLAMBDA', {'R_CONVERGENCE':1e-16})
mol = psi4.core.get_active_molecule()
ccsd = CCEnergy(mol, memory=2)
ccsd.compute_ccsd()
#hbar = CCHbar(ccsd)
Lambda = CCLambda(ccsd)
Lambda.compute_lambda()
#Lambda = 0
#density = 0
#density = CCDensity(ccsd,Lambda)
options = {
'timestep' : 0.1,
'number of steps' : 1000,
'timelength' : np.inf,
'field amplitude' : 0.002,
'field frequency' : 0.5}
def test_input_example_2():
"""Run a FCISCF computation on methylene using ROHF orbitals optimized for the 3B1 state.
Computes both the lowest 3B1 and 1A1 states."""
import math
import psi4
import forte
import pytest
ref_e_1a1 = -38.900217662950
ref_e_3b1 = -38.960623289646
psi4.geometry("""
0 3
C
H 1 1.085
H 1 1.085 2 135.5
""")
psi4.set_options({'basis': 'DZ', 'scf_type': 'pk', 'e_convergence': 12, 'reference': 'rohf'})
psi4.set_module_options(
'FORTE', {
'job_type': 'mcscf_two_step',
'active_space_solver': 'fci',
'restricted_docc': [1, 0, 0, 0],
'active': [3, 0, 2, 2],
'avg_state': [[2, 3, 1], [0, 1, 1]]
}
)
psi4.energy('forte')
assert psi4.core.variable('ENERGY ROOT 0 3B1') == pytest.approx(ref_e_3b1, 1.0e-9)
assert psi4.core.variable('ENERGY ROOT 0 1A1') == pytest.approx(ref_e_1a1, 1.0e-9)
def test_frozen_cart_h2o():
h2o = psi4.geometry("""
O 1.000000 1.000000 1.000000
H 2.000000 1.000000 1.000000
H 1.000000 2.000000 1.000000
units angstrom
no_com
no_reorient
""")
psi4.core.clean_options()
psi4_options = {
"basis": "cc-pvdz",
"reference": "rhf",
"scf_type": "df",
"max_energy_g_convergence": 7
}
psi4.set_options(psi4_options)
psi4.set_module_options("OPTKING", {"frozen_cartesian": """1 xyz"""})
json_output = optking.optimize_psi4("hf")
thisenergy = json_output["energies"][-1]
assert psi4.compare_values(-76.0270327834836, thisenergy, 6, "RHF Energy")
assert psi4.compare_values(h2o.x(0), 1.88972613289, 6,
"X Frozen coordinate")
assert psi4.compare_values(h2o.y(0), 1.88972613289, 6,
"Y Frozen coordinate")
assert psi4.compare_values(h2o.z(0), 1.88972613289, 6,
"Z Frozen coordinate")
def test_hooh_fixed_OOH_bend():
# Constrained minimization with O-O-H angles fixed to reach eq. at 105.0 degrees.
hooh = psi4.geometry("""
H
O 1 0.90
O 2 1.40 1 100.0
H 3 0.90 2 100.0 1 115.0
""")
psi4.set_options({
'diis': 'false',
'basis': 'cc-pvdz',
'g_convergence': 'gau_verytight'
})
#fixed_distance = (" ")
bend_coordinates = ("""
1 2 3 105.0
2 3 4 105.0
""")
psi4.set_module_options('Optking', {'fixed_bend': bend_coordinates})
Psi4Opt.calcName = 'hf'
thisenergy = Psi4Opt.Psi4Opt()
assert psi4.compare_values(
OOH_105_bend, thisenergy, 6,
"Int. Coord. RHF opt of HOOH with O-O-H fixed to 105, energy") #TEST
def test_hess_every3():
hooh = psi4.geometry("""
H
O 1 0.9
O 2 1.4 1 100.0
H 3 0.9 2 100.0 1 170.0
""")
#set optking full_hess_every 3
psi4.set_options({
'basis': 'cc-pvdz',
'g_convergence': 'gau_verytight',
'scf_type': 'pk',
})
psi4.set_module_options('Optking', {
'full_hess_every': 3,
'geom_maxiter': 200
})
#reload(Psi4Opt)
Psi4Opt.calcName = 'hf'
E = Psi4Opt.Psi4Opt()
assert psi4.compare_values(finalEnergy, E, 8,
"Final energy, every 3rd step Hessian") #TEST
def test_linesearch():
Ar2 = psi4.geometry("""
Ar
Ar 1 5.0
""")
psi4.core.clean_options()
psi4_options = {
'basis': 'cc-pvdz',
'd_convergence': 10,
'geom_maxiter': 20,
'g_convergence': 'gau_tight'
}
psi4.set_options(psi4_options)
# For some reason this works but setting it through set_options throws an error
psi4.set_module_options("OPTKING", {"step_type": "linesearch"})
json_output = optking.optimize_psi4('mp2')
E = json_output['energies'][-1]
nucenergy = json_output['trajectory'][-1]['properties'][
'nuclear_repulsion_energy']
assert psi4.compare_values(nucenergy, nucenergy, 3,
"Nuclear repulsion energy") #TEST
assert psi4.compare_values(refenergy, E, 1, "Reference energy") #TEST
def test_frozen_cart_h2o():
h2o = psi4.geometry("""
O 1.000000 1.000000 1.000000
H 2.000000 1.000000 1.000000
H 1.000000 2.000000 1.000000
units angstrom
no_com
no_reorient
""")
psi4.core.clean_options()
psi4_options = {
'basis': 'cc-pvdz',
'reference': 'rhf',
'scf_type': 'df',
'max_energy_g_convergence': 7
}
psi4.set_options(psi4_options)
psi4.set_module_options("OPTKING", {'frozen_cartesian': '''1 xyz'''})
json_output = optking.optimize_psi4('hf')
thisenergy = json_output['energies'][-1]
assert psi4.compare_values(-76.0270327834836, thisenergy, 6, "RHF Energy")
assert psi4.compare_values(h2o.x(0), 1.88972613289, 6,
"X Frozen coordinate")
assert psi4.compare_values(h2o.y(0), 1.88972613289, 6,
"Y Frozen coordinate")
assert psi4.compare_values(h2o.z(0), 1.88972613289, 6,
"Z Frozen coordinate")
def test_hooh_freeze_xyz_Hs(options, expected):
hooh = psi4.geometry("""
H 0.90 0.80 0.5
O 0.00 0.70 0.0
O 0.00 -0.70 0.0
H -0.90 -0.80 0.5
""")
psi4.core.clean_options()
psi4_options = {
'basis': 'cc-pvdz',
'opt_coordinates': 'cartesian',
'g_convergence': 'gau_tight',
'geom_maxiter': 20,
'consecutive_backsteps': 1
}
psi4.set_options(psi4_options)
psi4.set_module_options("OPTKING", options)
json_output = optking.optimize_psi4('hf')
thisenergy = json_output['energies'][-1] #TEST
assert psi4.compare_values(expected, thisenergy, 6) #TEST
def disabled_test_forte():
"""aci-10: Perform aci on benzyne"""
import forte
refscf = -229.20378006852584
refaci = -229.359450812283
refacipt2 = -229.360444943286
mbenzyne = psi4.geometry("""
0 1
C 0.0000000000 -2.5451795941 0.0000000000
C 0.0000000000 2.5451795941 0.0000000000
C -2.2828001669 -1.3508352528 0.0000000000
C 2.2828001669 -1.3508352528 0.0000000000
C 2.2828001669 1.3508352528 0.0000000000
C -2.2828001669 1.3508352528 0.0000000000
H -4.0782187459 -2.3208602146 0.0000000000
H 4.0782187459 -2.3208602146 0.0000000000
H 4.0782187459 2.3208602146 0.0000000000
H -4.0782187459 2.3208602146 0.0000000000
units bohr
""")
psi4.set_options({
'basis': 'DZ',
'df_basis_mp2': 'cc-pvdz-ri',
'reference': 'uhf',
'scf_type': 'pk',
'd_convergence': 10,
'e_convergence': 12,
'guess': 'gwh',
})
psi4.set_module_options("FORTE", {
'root_sym': 0,
'frozen_docc': [2,1,0,0,0,0,2,1],
'restricted_docc': [3,2,0,0,0,0,2,3],
'active': [1,0,1,2,1,2,1,0],
'multiplicity': 1,
'aci_nroot': 1,
'job_type': 'aci',
'sigma': 0.001,
'aci_select_type': 'aimed_energy',
'aci_spin_projection': 1,
'aci_enforce_spin_complete': True,
'aci_add_aimed_degenerate': False,
'aci_project_out_spin_contaminants': False,
'diag_algorithm': 'full',
'aci_quiet_mode': True,
})
scf = psi4.energy('scf')
assert psi4.compare_values(refscf, scf,10,"SCF Energy")
psi4.energy('forte')
assert psi4.compare_values(refaci, psi4.variable("ACI ENERGY"),10,"ACI energy")
assert psi4.compare_values(refacipt2, psi4.variable("ACI+PT2 ENERGY"),8,"ACI+PT2 energy")
def test_optrot():
psi4.core.clean()
# Set memory
psi4.set_memory('2 GB')
psi4.core.set_output_file('test_optrot_out.dat', False)
np.set_printoptions(precision=12, threshold=np.inf, linewidth=200, suppress=True)
# Set Psi4 options
mol = psi4.geometry("""
O -0.028962160801 -0.694396279686 -0.049338350190
O 0.028962160801 0.694396279686 -0.049338350190
H 0.350498145881 -0.910645626300 0.783035421467
H -0.350498145881 0.910645626300 0.783035421467
symmetry c1
""")
psi4.set_options({'basis': 'cc-pVDZ', 'scf_type': 'pk',
'freeze_core': 'false', 'e_convergence': 1e-10,
'd_convergence': 1e-10, 'save_jk': 'true'})
# Set for CCSD
E_conv = 1e-10
R_conv = 1e-10
maxiter = 40
compare_psi4 = False
# Set for LPNO
#local=True
local=False
pno_cut = 0.0
# Set for polarizability calculation
typ = 'polar'
omega_nm = 589.0
# Compute RHF energy with psi4
psi4.set_module_options('SCF', {'E_CONVERGENCE': 1e-10})
psi4.set_module_options('SCF', {'D_CONVERGENCE': 1e-10})
e_scf, wfn = psi4.energy('SCF', return_wfn=True)
print('SCF energy: {}\n'.format(e_scf))
print('Nuclear repulsion energy: {}\n'.format(mol.nuclear_repulsion_energy()))
# Create Helper_CCenergy object
optrot_lg = ccsd_lpno.do_linresp(wfn, omega_nm, mol, method='optrot', gauge='length', e_conv=E_conv, r_conv=R_conv, localize=local, pno_cut=pno_cut)
optrot_mvg = ccsd_lpno.do_linresp(wfn, omega_nm, mol, method='optrot', gauge='velocity', e_conv=E_conv, r_conv=R_conv, localize=local, pno_cut=pno_cut)
# Comaprison with Psi4
psi4.set_options({'e_convergence': 1e-10})
psi4.set_options({'r_convergence': 1e-10})
psi4.set_options({'omega': [589, 'nm'],
'gauge': 'both'})
psi4.properties('ccsd', properties=['rotation'], ref_wfn=wfn)
psi4.compare_values(optrot_lg, psi4.core.variable("CCSD SPECIFIC ROTATION (LEN) @ 589NM"), \
4, "CCSD SPECIFIC ROTATION (LENGTH GAUGE) 589 nm") #TEST
psi4.compare_values(optrot_mvg, psi4.core.variable("CCSD SPECIFIC ROTATION (MVG) @ 589NM"), \
4, "CCSD SPECIFIC ROTATION (MODIFIED VELOCITY GAUGE) 589 nm") #TEST
def surf_psi4(params, output_file):
natoms = params.natoms
geom = params.geometry
#print(geom)
geom += "symmetry c1\n"
geom += "no_reorient\n"
geom += "no_com"
#print(geom)
#print(geom)
mol = psi4.geometry(geom)
if (params.constraint_type == 'angle'):
coord_constraint = 'fixed_bend'
if (params.constraint_type == 'bond'):
coord_constraint = 'fixed_distance'
if (params.constraint_type == 'dihedral'):
coord_constraint = 'fixed_dihedral'
output = open(output_file, "a")
output.write(
'\n\n--%s surface scan for fixed %s of atoms %s--\n' %
(params.scan_type, params.constraint_type, params.constrained_atoms))
output.write(
'\n--------------------------------------------------------------------------------------\n'
)
output.write('\n{:>20} {:>20}\n'.format('Coordinate', 'E'))
output.write(
'-------------------------------------------------------------------------------------\n'
)
output.close()
surf_out = open("surface_scan.xyz", "w+")
surf_out.close()
for constrained_value in params.constrained_values:
#print(params.constrained_values)
fixed_coord = params.constrained_atoms + str(constrained_value)
#print(fixed_coord)
psi4.set_options(params.keywords)
psi4.set_module_options('Optking', {coord_constraint: fixed_coord})
psi4.set_num_threads(params.nthreads)
psi4.core.set_output_file(
"psi4_output/surf_%.2f.out" % constrained_value, False)
surf_out = open("surface_scan.xyz", "a")
surf_out.write("%s\n" % natoms)
surf_out.write(
"%s surface scan with fixed %s of %f\n" %
(params.scan_type, params.constraint_type, constrained_value))
if (params.scan_type == 'relaxed'):
E = psi4.optimize("%s/%s" % (params.method, params.basis))
pre_string = mol.create_psi4_string_from_molecule()
#print(pre_string)
struct = pre_string.split("\n", 7)[7]
#print(struct)
surf_out.write(struct[:-1])
if (params.scan_type == 'unrelaxed'):
E = psi4.energy("%s/%s" % (params.method, params.basis))
output = open(output_file, "a")
output.write('\n{:>20.4f} {:>20.7f}\n'.format(constrained_value, E))
output.close()
def test_v2rdm_casscf():
"""v2rdm_casscf/tests/v2rdm1"""
#! cc-pvdz N2 (6,6) active space Test DQG
print(
' N2 / cc-pVDZ / DQG(6,6), scf_type = CD / 1e-12, rNN = 0.5 A')
import v2rdm_casscf
n2 = psi4.geometry("""
0 1
n
n 1 r
""")
interloper = psi4.geometry("""
0 1
O
H 1 1.0
H 1 1.0 2 90.0
""")
psi4.set_options({
'basis': 'cc-pvdz',
'scf_type': 'cd',
'cholesky_tolerance': 1e-12,
'd_convergence': 1e-10,
'maxiter': 500,
'restricted_docc': [2, 0, 0, 0, 0, 2, 0, 0],
'active': [1, 0, 1, 1, 0, 1, 1, 1],
})
psi4.set_module_options(
'v2rdm_casscf',
{
'positivity': 'dqg',
'r_convergence': 1e-5,
'e_convergence': 1e-6,
'maxiter': 20000,
#'orbopt_frequency': 1000,
#'mu_update_frequency': 1000,
})
psi4.activate(n2)
n2.r = 0.5 * 0.52917721067 / 0.52917720859
refscf = -103.04337420425350
refv2rdm = -103.086205379481
psi4.energy('v2rdm-casscf', molecule=n2)
assert psi4.compare_values(refscf, psi4.variable("SCF TOTAL ENERGY"), 8,
"SCF total energy")
assert psi4.compare_values(refv2rdm, psi4.variable("CURRENT ENERGY"), 5,
"v2RDM-CASSCF total energy")
def test_v2rdm_casscf():
"""v2rdm_casscf/tests/v2rdm1"""
#! cc-pvdz N2 (6,6) active space Test DQG
print(' N2 / cc-pVDZ / DQG(6,6), scf_type = CD / 1e-12, rNN = 0.5 A')
import v2rdm_casscf
n2 = psi4.geometry("""
0 1
n
n 1 r
""")
interloper = psi4.geometry("""
0 1
O
H 1 1.0
H 1 1.0 2 90.0
""")
psi4.set_options({
'basis': 'cc-pvdz',
'scf_type': 'cd',
'cholesky_tolerance': 1e-12,
'd_convergence': 1e-10,
'maxiter': 500,
'restricted_docc': [ 2, 0, 0, 0, 0, 2, 0, 0 ],
'active': [ 1, 0, 1, 1, 0, 1, 1, 1 ],
})
psi4.set_module_options('v2rdm_casscf', {
'positivity': 'dqg',
'r_convergence': 1e-5,
'e_convergence': 1e-6,
'maxiter': 20000,
#'orbopt_frequency': 1000,
#'mu_update_frequency': 1000,
})
psi4.activate(n2)
n2.r = 0.5 * 0.52917721067 / 0.52917720859
refscf = -103.04337420425350
refv2rdm = -103.086205379481
psi4.energy('v2rdm-casscf', molecule=n2)
assert psi4.compare_values(refscf, psi4.variable("SCF TOTAL ENERGY"), 8, "SCF total energy")
assert psi4.compare_values(refv2rdm, psi4.variable("CURRENT ENERGY"), 5, "v2RDM-CASSCF total energy")
def run_hf(xyz,
basis,
charge=0,
multiplicity=1,
conv_tol=1e-11,
conv_tol_grad=1e-8,
max_iter=150,
pe_options=None):
basissets = {
"sto3g": "sto-3g",
"def2tzvp": "def2-tzvp",
"ccpvdz": "cc-pvdz",
}
# needed for PE and PCM tests
psi4.core.clean_options()
mol = psi4.geometry(f"""
{charge} {multiplicity}
{xyz}
symmetry c1
units au
no_reorient
no_com
""")
psi4.core.be_quiet()
psi4.set_options({
'basis': basissets.get(basis, basis),
'scf_type': 'pk',
'e_convergence': conv_tol,
'd_convergence': conv_tol_grad,
'maxiter': max_iter,
'reference': "RHF",
})
if pe_options:
psi4.set_options({"pe": "true"})
psi4.set_module_options("pe", {"potfile": pe_options["potfile"]})
if multiplicity != 1:
psi4.set_options({
'reference': "UHF",
'maxiter': max_iter + 500,
'soscf': 'true'
})
_, wfn = psi4.energy('SCF', return_wfn=True, molecule=mol)
psi4.core.clean()
return wfn
def test_input_simple():
"""Test input for a simple computation using the `ROOT_SYM` keyword."""
import math
import psi4
import forte
import pytest
psi4.geometry("""
Li
H 1 3.0
units bohr
""")
ref_efci_0 = -8.008550659909
ref_efci_1 = -7.396156201698
ref_efci_2 = -7.853436217184
ref_efci_3 = -7.853436217157
# need to clean the options otherwise this job will interfere
forte.clean_options()
psi4.set_options({'basis': 'DZ', 'scf_type': 'pk', 'e_convergence': 12})
psi4.set_module_options(
'FORTE', {
'active_space_solver': 'fci',
'active': [8, 0, 2, 2],
'restricted_docc': [0, 0, 0, 0],
'root_sym': 0,
'multiplicity' : 1,
'ms': 0.0
}
)
psi4.core.set_output_file('debug.txt',False)
efci = psi4.energy('forte')
print('Test 1')
assert efci == pytest.approx(ref_efci_0, 1.0e-9)
print('Test 2')
psi4.set_module_options('FORTE', {
'root_sym': 1,
})
efci = psi4.energy('forte')
assert efci == pytest.approx(ref_efci_1, 1.0e-9)
psi4.set_module_options('FORTE', {
'root_sym': 2,
})
efci = psi4.energy('forte')
assert efci == pytest.approx(ref_efci_2, 1.0e-9)
psi4.set_module_options('FORTE', {
'root_sym': 3,
})
efci = psi4.energy('forte')
assert efci == pytest.approx(ref_efci_3, 1.0e-9)
def test_v2rdm6():
#! cc-pvdz N2 (6,6) active space Test DQG
print(' N2 / cc-pVDZ / DQG(6,6), geometry optimization')
import psi4
n2 = psi4.geometry("""
0 1
n
n 1 1.1
""")
psi4.set_options({
'basis': 'cc-pvdz',
'scf_type': 'pk',
'd_convergence': 1e-10,
'maxiter': 500,
'restricted_docc': [2, 0, 0, 0, 0, 2, 0, 0],
'active': [1, 0, 1, 1, 0, 1, 1, 1],
})
psi4.set_module_options(
'v2rdm_casscf',
{
'positivity': 'dqg',
#'r_convergence': 1e-7,
'r_convergence': 1e-6,
'e_convergence': 1e-5,
'orbopt_gradient_convergence': 1e-8,
'maxiter': 20000,
})
psi4.activate(n2)
psi4.optimize('v2rdm-casscf')
refnuc = 23.1968666562054260
refscf = -108.95016246035139
refv2rdm = -109.095505119442
assert psi4.compare_values(refnuc, n2.nuclear_repulsion_energy(), 4,
"Nuclear repulsion energy")
assert psi4.compare_values(refscf, psi4.variable("SCF TOTAL ENERGY"), 5,
"SCF total energy")
assert psi4.compare_values(refv2rdm, psi4.variable("CURRENT ENERGY"), 4,
"v2RDM-CASSCF total energy")
def test_v2rdm():
#! cc-pvdz N2 (6,6) active space Test DQG
print(' N2 / cc-pVDZ / DQG(6,6), scf_type = DF, rNN = 1.1 A')
import psi4
import sys
sys.path.insert(0, '../..')
import hilbert
n2 = psi4.geometry("""
0 1
n
n 1 r
""")
psi4.set_options({
'basis': 'cc-pvdz',
'scf_type': 'df',
'd_convergence': 1e-10,
'maxiter': 500,
'restricted_docc': [2, 0, 0, 0, 0, 2, 0, 0],
'active': [1, 0, 1, 1, 0, 1, 1, 1],
})
psi4.set_module_options(
'hilbert', {
'positivity': 'dqg',
'r_convergence': 1e-5,
'e_convergence': 1e-6,
'maxiter': 20000,
})
psi4.activate(n2)
n2.r = 1.1
refscf = -108.95348837831371
refv2rdm = -109.094404909477
psi4.energy('v2rdm-casscf')
assert psi4.compare_values(refscf, psi4.variable("SCF TOTAL ENERGY"), 8,
"SCF total energy")
assert psi4.compare_values(refv2rdm, psi4.variable("CURRENT ENERGY"), 5,
"v2RDM-CASSCF total energy")
def test_v2rdm8():
# H2 / cc-pVDZ / D(2,2), scf_type = DF, rHH = 1.0 A
print(' H2 / cc-pVDZ / D(2,2), scf_type = DF, rHH = 1.0 A')
import v2rdm_casscf
import psi4
h2 = psi4.geometry("""
0 1
h
h 1 r
symmetry c1
""")
psi4.set_options({
"basis": "cc-pvdz",
"mcscf_type": "df",
"scf_type": "df",
"d_convergence": 1e-10,
"maxiter": 500,
"restricted_docc": [0],
"restricted_uocc": [8],
"active": [2],
})
psi4.set_module_options(
'v2rdm_casscf', {
"positivity": "d",
"r_convergence": 1e-6,
"e_convergence": 1e-8,
"maxiter": 20000,
})
psi4.activate(h2)
h2.r = 1.0
psi4.set_options({"df_ints_io": "save"})
en, wfn = psi4.energy('scf', return_wfn=True)
en1 = v2rdm_casscf.v2rdm_scf_solver(wfn)
en2 = psi4.energy('casscf')
assert psi4.compare_values(en1, en2, 6, "v2RDM-CASSCF total energy")
def test_h2o_rfo():
h2o = psi4.geometry("""
O
H 1 1.0
H 1 1.0 2 104.5
""")
psi4.set_options({
'basis': 'cc-pvtz',
'e_convergence': '10',
'd_convergence': '10',
'scf_type': 'pk',
})
psi4.set_module_options('Optking', {'step_type': 'rfo'})
Psi4Opt.calcName = 'hf'
E = Psi4Opt.Psi4Opt()
assert psi4.compare_values(finalEnergy, E, 6,
"RFO Step Final Energy") #TEST
def v2rdm_pyscf():
# pyscf reference
np.set_printoptions(linewidth=500)
basis = 'STO-3G'
mol = pyscf.M(
atom='B 0 0 0; H 0 0 {}'.format(1.1),
basis=basis)
mf = mol.RHF()
mf.verbose = 3
mf.run()
# make h1 and spatial integrals in MO basis
eri = ao2mo.kernel(mol, mf.mo_coeff)
eri = ao2mo.restore(1, eri, mf.mo_coeff.shape[1])
# this produces spatial MO h1 integrals
h1 = reduce(np.dot, (mf.mo_coeff.T, mf.get_hcore(), mf.mo_coeff))
# these parameters are hard-coded for now
nalpha = 3
nbeta = 3
nmo = 6
# hilbert options
psi4.set_module_options('hilbert', {
#'sdp_solver': 'rrsdp',
'positivity': 'dqg',
'r_convergence': 1e-5,
'e_convergence': 1e-4,
'maxiter': 20000,
})
# grab options object
options = psi4.core.get_options()
options.set_current_module('HILBERT')
v2rdm_pyscf = hilbert.v2RDMHelper(nalpha,nbeta,nmo,h1.flatten(),eri.flatten(),options)
current_energy = v2rdm_pyscf.compute_energy()
return current_energy
def test_v2rdm5():
#! cc-pvdz N2 (6,6) active space Test DQG
print(' N2 / cc-pVDZ / DQG+T2(6,6), scf_type = PK, rNN = 1.1 A')
import psi4
n2 = psi4.geometry("""
0 1
n
n 1 r
""")
psi4.set_options({
'basis': 'cc-pvdz',
'scf_type': 'pk',
'd_convergence': 1e-10,
'maxiter': 500,
'restricted_docc': [2, 0, 0, 0, 0, 2, 0, 0],
'active': [1, 0, 1, 1, 0, 1, 1, 1],
})
psi4.set_module_options(
'v2rdm_casscf', {
'positivity': 'dqgt2',
'r_convergence': 1e-4,
'e_convergence': 5e-4,
'maxiter': 20000,
})
psi4.activate(n2)
n2.r = 1.1
refscf = -108.95379624015767
refv2rdm = -109.091487394061
psi4.energy('v2rdm-casscf')
assert psi4.compare_values(refscf, psi4.variable("SCF TOTAL ENERGY"), 8,
"SCF total energy")
assert psi4.compare_values(refv2rdm, psi4.variable("CURRENT ENERGY"), 4,
"v2RDM-CASSCF total energy")
def __init__(self, mol, freeze_core=False, memory=2):
if freeze_core:
raise Exception("Frozen core doesnt work yet!")
print("\nInitalizing CCSD object...\n")
# Integral generation from Psi4's MintsHelper
time_init = time.time()
print('Computing RHF reference.')
psi4.core.set_active_molecule(mol)
psi4.set_module_options('SCF', {'SCF_TYPE': 'PK'})
psi4.set_module_options('SCF', {'E_CONVERGENCE': 10e-10})
psi4.set_module_options('SCF', {'D_CONVERGENCE': 10e-10})
# Core is frozen by default
if not freeze_core:
psi4.set_module_options('CCENERGY', {'FREEZE_CORE': 'FALSE'})
self.rhf_e, self.wfn = psi4.energy('SCF', return_wfn=True)
print('RHF Final Energy % 16.10f\n' % (self.rhf_e))
self.ccsd_corr_e = 0.0
self.ccsd_e = 0.0
self.eps = np.asarray(self.wfn.epsilon_a())
self.ndocc = self.wfn.doccpi()[0]
self.nmo = self.wfn.nmo()
self.memory = memory
self.nfzc = 0
# Freeze core
if freeze_core:
Zlist = np.array([mol.Z(x) for x in range(mol.natom())])
self.nfzc = np.sum(Zlist > 2)
self.nfzc += np.sum(Zlist > 10) * 4
if np.any(Zlist > 18):
raise Exception("Frozen core for Z > 18 not yet implemented")
print("Cutting %d core orbitals." % self.nfzc)
# Copy C
oldC = np.array(self.wfn.Ca(), copy=True)
# Build new C matrix and view, set with numpy slicing
self.C = psi.Matrix(self.nmo, self.nmo - self.nfzc)
self.npC = np.asarray(self.C)
self.npC[:] = oldC[:, self.nfzc:]
# Update epsilon array
self.ndocc -= self.nfzc
else:
self.C = self.wfn.Ca()
self.npC = np.asarray(self.C)
mints = psi4.core.MintsHelper(self.wfn.basisset())
H = np.asarray(mints.ao_kinetic()) + np.asarray(mints.ao_potential())
self.nmo = H.shape[0]
# Update H, transform to MO basis and tile for alpha/beta spin
H = np.einsum('uj,vi,uv', self.npC, self.npC, H)
H = np.repeat(H, 2, axis=0)
H = np.repeat(H, 2, axis=1)
# Make H block diagonal
spin_ind = np.arange(H.shape[0], dtype=np.int) % 2
H *= (spin_ind.reshape(-1, 1) == spin_ind)
#Make spin-orbital MO
print('Starting AO -> spin-orbital MO transformation...')
ERI_Size = (self.nmo**4) * 128.e-9
memory_footprint = ERI_Size * 5
if memory_footprint > self.memory:
psi.clean()
raise Exception("Estimated memory utilization (%4.2f GB) exceeds numpy_memory \
limit of %4.2f GB." % (memory_footprint, self.memory))
# Integral generation from Psi4's MintsHelper
self.MO = np.asarray(mints.mo_spin_eri(self.C, self.C))
print("Size of the ERI tensor is %4.2f GB, %d basis functions." % (ERI_Size, self.nmo))
# Update nocc and nvirt
self.nso = self.nmo * 2
self.nfzc = self.nfzc * 2
self.nocc = self.ndocc * 2
self.nvirt = self.nso - self.nocc - self.nfzc * 2
# Make slices
self.slice_nfzc = slice(0, self.nfzc)
self.slice_o = slice(self.nfzc, self.nocc + self.nfzc)
self.slice_v = slice(self.nocc + self.nfzc, self.nso)
self.slice_a = slice(0, self.nso)
self.slice_dict = {'f': self.slice_nfzc, 'o': self.slice_o, 'v': self.slice_v, 'a': self.slice_a}
#Extend eigenvalues
self.eps = np.repeat(self.eps, 2)
# Compute Fock matrix
self.F = H + np.einsum('pmqm->pq', self.MO[:, self.slice_o, :, self.slice_o])
### Build D matrices
print('\nBuilding denominator arrays...')
Focc = np.diag(self.F)[self.slice_o]
Fvir = np.diag(self.F)[self.slice_v]
self.Dia = Focc.reshape(-1, 1) - Fvir
self.Dijab = Focc.reshape(-1, 1, 1, 1) + Focc.reshape(-1, 1, 1) - Fvir.reshape(-1, 1) - Fvir
### Construct initial guess
print('Building initial guess...')
# t^a_i
self.t1 = np.zeros((self.nocc, self.nvirt))
# t^{ab}_{ij}
self.t2 = self.MO[self.slice_o, self.slice_o, self.slice_v, self.slice_v] / self.Dijab
print('\n..initialed CCSD in %.3f seconds.\n' % (time.time() - time_init))
def _test_scf5():
"""scf5"""
#! Test of all different algorithms and reference types for SCF, on singlet and triplet O2, using the cc-pVTZ basis set and using ERD integrals.
print(' Case Study Test of all SCF algorithms/spin-degeneracies: Singlet-Triplet O2')
print(' -Integral package: {}'.format(psi4.core.get_global_option('integral_package')))
#Ensure that the checkpoint file is always nuked
psi4.core.IOManager.shared_object().set_specific_retention(32,False)
Eref_nuc = 30.7884922572
Eref_sing_can = -149.58723684929720
Eref_sing_df = -149.58715054487624
Eref_uhf_can = -149.67135517240553
Eref_uhf_df = -149.67125624291961
Eref_rohf_can = -149.65170765757173
Eref_rohf_df = -149.65160796208073
singlet_o2 = psi4.geometry("""
0 1
O
O 1 1.1
units angstrom
""")
triplet_o2 = psi4.geometry("""
0 3
O
O 1 1.1
units angstrom
""")
singlet_o2.update_geometry()
triplet_o2.update_geometry()
print(' -Nuclear Repulsion:')
assert psi4.compare_values(Eref_nuc, triplet_o2.nuclear_repulsion_energy(), 9, "Triplet nuclear repulsion energy")
assert psi4.compare_values(Eref_nuc, singlet_o2.nuclear_repulsion_energy(), 9, "Singlet nuclear repulsion energy")
psi4.set_options({
'basis': 'cc-pvtz',
'df_basis_scf': 'cc-pvtz-jkfit',
'print': 2})
print(' -Singlet RHF:')
psi4.set_module_options('scf', {'reference': 'rhf'})
psi4.set_module_options('scf', {'scf_type': 'pk'})
E = psi4.energy('scf', molecule=singlet_o2)
assert psi4.compare_values(Eref_sing_can, E, 6, 'Singlet PK RHF energy')
psi4.set_module_options('scf', {'scf_type': 'direct'})
E = psi4.energy('scf', molecule=singlet_o2)
assert psi4.compare_values(Eref_sing_can, E, 6, 'Singlet Direct RHF energy')
psi4.set_module_options('scf', {'scf_type': 'out_of_core'})
E = psi4.energy('scf', molecule=singlet_o2)
assert psi4.compare_values(Eref_sing_can, E, 6, 'Singlet Disk RHF energy')
psi4.set_module_options('scf', {'scf_type': 'df'})
E = psi4.energy('scf', molecule=singlet_o2)
assert psi4.compare_values(Eref_sing_df, E, 6, 'Singlet DF RHF energy')
print(' -Singlet UHF:')
psi4.set_module_options('scf', {'reference': 'uhf'})
psi4.set_module_options('scf', {'scf_type': 'pk'})
E = psi4.energy('scf', molecule=singlet_o2)
assert psi4.compare_values(Eref_sing_can, E, 6, 'Singlet PK UHF energy')
psi4.set_module_options('scf', {'scf_type': 'direct'})
E = psi4.energy('scf', molecule=singlet_o2)
assert psi4.compare_values(Eref_sing_can, E, 6, 'Singlet Direct UHF energy')
psi4.set_module_options('scf', {'scf_type': 'out_of_core'})
E = psi4.energy('scf', molecule=singlet_o2)
assert psi4.compare_values(Eref_sing_can, E, 6, 'Singlet Disk UHF energy')
psi4.set_module_options('scf', {'scf_type': 'df'})
E = psi4.energy('scf', molecule=singlet_o2)
assert psi4.compare_values(Eref_sing_df, E, 6, 'Singlet DF UHF energy')
print(' -Singlet CUHF:')
psi4.set_module_options('scf', {'reference': 'cuhf'})
psi4.set_module_options('scf', {'scf_type': 'pk'})
E = psi4.energy('scf', molecule=singlet_o2)
assert psi4.compare_values(Eref_sing_can, E, 6, 'Singlet PK CUHF energy')
psi4.set_module_options('scf', {'scf_type': 'direct'})
E = psi4.energy('scf', molecule=singlet_o2)
assert psi4.compare_values(Eref_sing_can, E, 6, 'Singlet Direct CUHF energy')
psi4.set_module_options('scf', {'scf_type': 'out_of_core'})
E = psi4.energy('scf', molecule=singlet_o2)
assert psi4.compare_values(Eref_sing_can, E, 6, 'Singlet Disk CUHF energy')
psi4.set_module_options('scf', {'scf_type': 'df'})
E = psi4.energy('scf', molecule=singlet_o2)
assert psi4.compare_values(Eref_sing_df, E, 6, 'Singlet DF CUHF energy')
psi4.set_options({
'basis': 'cc-pvtz',
'df_basis_scf': 'cc-pvtz-jkfit',
'guess': 'core',
'print': 2})
print(' -Triplet UHF:')
psi4.set_module_options('scf', {'reference': 'uhf'})
psi4.set_module_options('scf', {'scf_type': 'pk'})
E = psi4.energy('scf', molecule=triplet_o2)
assert psi4.compare_values(Eref_uhf_can, E, 6, 'Triplet PK UHF energy')
psi4.set_module_options('scf', {'scf_type': 'direct'})
E = psi4.energy('scf', molecule=triplet_o2)
assert psi4.compare_values(Eref_uhf_can, E, 6, 'Triplet Direct UHF energy')
psi4.set_module_options('scf', {'scf_type': 'out_of_core'})
E = psi4.energy('scf', molecule=triplet_o2)
assert psi4.compare_values(Eref_uhf_can, E, 6, 'Triplet Disk UHF energy')
psi4.set_module_options('scf', {'scf_type': 'df'})
E = psi4.energy('scf', molecule=triplet_o2)
assert psi4.compare_values(Eref_uhf_df, E, 6, 'Triplet DF UHF energy')
psi4.core.clean()
print(' -Triplet ROHF:')
psi4.set_module_options('scf', {'reference': 'rohf'})
psi4.set_module_options('scf', {'scf_type': 'pk'})
E = psi4.energy('scf', molecule=triplet_o2)
assert psi4.compare_values(Eref_rohf_can, E, 6, 'Triplet PK ROHF energy')
psi4.core.clean()
psi4.set_module_options('scf', {'scf_type': 'direct'})
E = psi4.energy('scf', molecule=triplet_o2)
assert psi4.compare_values(Eref_rohf_can, E, 6, 'Triplet Direct ROHF energy')
psi4.core.clean()
psi4.set_module_options('scf', {'scf_type': 'out_of_core'})
E = psi4.energy('scf', molecule=triplet_o2)
assert psi4.compare_values(Eref_rohf_can, E, 6, 'Triplet Disk ROHF energy')
psi4.core.clean()
psi4.set_module_options('scf', {'scf_type': 'df'})
E = psi4.energy('scf', molecule=triplet_o2)
assert psi4.compare_values(Eref_rohf_df, E, 6, 'Triplet DF ROHF energy')
psi4.core.clean()
print(' -Triplet CUHF:')
psi4.set_module_options('scf', {'reference': 'cuhf'})
psi4.set_module_options('scf', {'scf_type': 'pk'})
E = psi4.energy('scf', molecule=triplet_o2)
assert psi4.compare_values(Eref_rohf_can, E, 6, 'Triplet PK CUHF energy')
psi4.core.clean()
psi4.set_module_options('scf', {'scf_type': 'direct'})
E = psi4.energy('scf', molecule=triplet_o2)
assert psi4.compare_values(Eref_rohf_can, E, 6, 'Triplet Direct CUHF energy')
psi4.core.clean()
psi4.set_module_options('scf', {'scf_type': 'out_of_core'})
E = psi4.energy('scf', molecule=triplet_o2)
assert psi4.compare_values(Eref_rohf_can, E, 6, 'Triplet Disk CUHF energy')
psi4.core.clean()
psi4.set_module_options('scf', {'scf_type': 'df'})
E = psi4.energy('scf', molecule=triplet_o2)
assert psi4.compare_values(Eref_rohf_df, E, 6, 'Triplet DF CUHF energy')