# Adjust the MPI schedular and scratch directory if needed. # NOTE the DMRG-NEVPT2 is expensive, it requires about 8 GB memory per processor # #from pyscf.dmrgscf import settings #settings.MPIPREFIX = 'srun' #settings.BLOCKSCRATCHDIR = '/scratch' from pyscf.dmrgscf.dmrgci import DMRGCI, DMRGSCF from pyscf.mrpt.nevpt2 import sc_nevpt # # Redirect output to another file # mol.build_(verbose=7, output = 'hs_dmrg.out') mf = scf.sfx2c1e(scf.RHF(mol)) mc = DMRGSCF(mf, norb, [nalpha,nbeta]) mc.chkfile = 'hs_mc.chk' mc.max_memory = 30000 mc.fcisolver.maxM = 1000 mc.fcisolver.tol = 1e-6 orbs = mc.sort_mo(caslst, coeff, base=0) mc.mc1step(orbs) # # CASCI-NEVPT2 # # If DMRG-CASSCF was finished without any problems (eg convergence, wall time # limits on cluster etc), one can simply continue with DMRG-NEVPT2 like # sc_nevpt(mc)
def test_init(self):
from pyscf import dft
from pyscf import x2c
mol_r = mol
mol_u = gto.M(atom='Li', spin=1, verbose=0)
mol_r1 = gto.M(atom='H', spin=1, verbose=0)
sym_mol_r = molsym
sym_mol_u = gto.M(atom='Li', spin=1, symmetry=1, verbose=0)
sym_mol_r1 = gto.M(atom='H', spin=1, symmetry=1, verbose=0)
self.assertTrue(isinstance(scf.RKS(mol_r), dft.rks.RKS))
self.assertTrue(isinstance(scf.RKS(mol_u), dft.roks.ROKS))
self.assertTrue(isinstance(scf.UKS(mol_r), dft.uks.UKS))
self.assertTrue(isinstance(scf.ROKS(mol_r), dft.roks.ROKS))
self.assertTrue(isinstance(scf.GKS(mol_r), dft.gks.GKS))
self.assertTrue(isinstance(scf.KS(mol_r), dft.rks.RKS))
self.assertTrue(isinstance(scf.KS(mol_u), dft.uks.UKS))
self.assertTrue(isinstance(scf.RHF(mol_r), scf.hf.RHF))
self.assertTrue(isinstance(scf.RHF(mol_u), scf.rohf.ROHF))
self.assertTrue(isinstance(scf.RHF(mol_r1), scf.rohf.ROHF))
self.assertTrue(isinstance(scf.UHF(mol_r), scf.uhf.UHF))
self.assertTrue(isinstance(scf.UHF(mol_u), scf.uhf.UHF))
self.assertTrue(isinstance(scf.UHF(mol_r1), scf.uhf.HF1e))
self.assertTrue(isinstance(scf.ROHF(mol_r), scf.rohf.ROHF))
self.assertTrue(isinstance(scf.ROHF(mol_u), scf.rohf.ROHF))
self.assertTrue(isinstance(scf.ROHF(mol_r1), scf.rohf.HF1e))
self.assertTrue(isinstance(scf.HF(mol_r), scf.hf.RHF))
self.assertTrue(isinstance(scf.HF(mol_u), scf.uhf.UHF))
self.assertTrue(isinstance(scf.HF(mol_r1), scf.rohf.HF1e))
self.assertTrue(isinstance(scf.GHF(mol_r), scf.ghf.GHF))
self.assertTrue(isinstance(scf.GHF(mol_u), scf.ghf.GHF))
self.assertTrue(isinstance(scf.GHF(mol_r1), scf.ghf.HF1e))
#TODO: self.assertTrue(isinstance(scf.DHF(mol_r), scf.dhf.RHF))
self.assertTrue(isinstance(scf.DHF(mol_u), scf.dhf.UHF))
self.assertTrue(isinstance(scf.DHF(mol_r1), scf.dhf.HF1e))
self.assertTrue(isinstance(scf.RHF(sym_mol_r), scf.hf_symm.RHF))
self.assertTrue(isinstance(scf.RHF(sym_mol_u), scf.hf_symm.ROHF))
self.assertTrue(isinstance(scf.RHF(sym_mol_r1), scf.hf_symm.HF1e))
self.assertTrue(isinstance(scf.UHF(sym_mol_r), scf.uhf_symm.UHF))
self.assertTrue(isinstance(scf.UHF(sym_mol_u), scf.uhf_symm.UHF))
self.assertTrue(isinstance(scf.UHF(sym_mol_r1), scf.uhf_symm.HF1e))
self.assertTrue(isinstance(scf.ROHF(sym_mol_r), scf.hf_symm.ROHF))
self.assertTrue(isinstance(scf.ROHF(sym_mol_u), scf.hf_symm.ROHF))
self.assertTrue(isinstance(scf.ROHF(sym_mol_r1), scf.hf_symm.HF1e))
self.assertTrue(isinstance(scf.HF(sym_mol_r), scf.hf_symm.RHF))
self.assertTrue(isinstance(scf.HF(sym_mol_u), scf.uhf_symm.UHF))
self.assertTrue(isinstance(scf.HF(sym_mol_r1), scf.hf_symm.ROHF))
self.assertTrue(isinstance(scf.GHF(sym_mol_r), scf.ghf_symm.GHF))
self.assertTrue(isinstance(scf.GHF(sym_mol_u), scf.ghf_symm.GHF))
self.assertTrue(isinstance(scf.GHF(sym_mol_r1), scf.ghf_symm.HF1e))
self.assertTrue(isinstance(scf.X2C(mol_r), x2c.x2c.UHF))
self.assertTrue(isinstance(scf.sfx2c1e(scf.HF(mol_r)), scf.rhf.RHF))
self.assertTrue(isinstance(scf.sfx2c1e(scf.HF(mol_u)), scf.uhf.UHF))
self.assertTrue(isinstance(scf.sfx2c1e(scf.HF(mol_r1)), scf.rohf.ROHF))
self.assertTrue(
isinstance(scf.sfx2c1e(scf.HF(sym_mol_r)), scf.rhf_symm.RHF))
self.assertTrue(
isinstance(scf.sfx2c1e(scf.HF(sym_mol_u)), scf.uhf_symm.UHF))
self.assertTrue(
isinstance(scf.sfx2c1e(scf.HF(sym_mol_r1)), scf.hf_symm.ROHF))
self.assertTrue(isinstance(scf.density_fit(scf.HF(mol_r)),
scf.rhf.RHF))
self.assertTrue(isinstance(scf.density_fit(scf.HF(mol_u)),
scf.uhf.UHF))
self.assertTrue(
isinstance(scf.density_fit(scf.HF(mol_r1)), scf.rohf.ROHF))
self.assertTrue(
isinstance(scf.density_fit(scf.HF(sym_mol_r)), scf.rhf_symm.RHF))
self.assertTrue(
isinstance(scf.density_fit(scf.HF(sym_mol_u)), scf.uhf_symm.UHF))
self.assertTrue(
isinstance(scf.density_fit(scf.HF(sym_mol_r1)), scf.hf_symm.ROHF))
self.assertTrue(isinstance(scf.newton(scf.HF(mol_r)), scf.rhf.RHF))
self.assertTrue(isinstance(scf.newton(scf.HF(mol_u)), scf.uhf.UHF))
self.assertTrue(isinstance(scf.newton(scf.HF(mol_r1)), scf.rohf.ROHF))
self.assertTrue(
isinstance(scf.newton(scf.HF(sym_mol_r)), scf.rhf_symm.RHF))
self.assertTrue(
isinstance(scf.newton(scf.HF(sym_mol_u)), scf.uhf_symm.UHF))
self.assertTrue(
isinstance(scf.newton(scf.HF(sym_mol_r1)), scf.hf_symm.ROHF))
the Hessian for the large-basis-density-fitted-scf scheme.
'''
mol = gto.Mole()
mol.build(
verbose = 0,
atom = '''8 0 0. 0
1 0 -0.757 0.587
1 0 0.757 0.587''',
basis = 'ccpvdz',
)
#
# 1. spin-free X2C-HF with density fitting approximation on 2E integrals
#
mf = scf.density_fit(scf.sfx2c1e(scf.RHF(mol)))
mf = scf.RHF(mol).x2c().density_fit() # Stream style
energy = mf.kernel()
print('E = %.12f, ref = -76.075408156180' % energy)
#
# 2. spin-free X2C correction for density-fitting HF. Since X2C correction is
# commutable with density fitting operation, it is fully equivalent to case 1.
#
mf = scf.sfx2c1e(scf.density_fit(scf.RHF(mol)))
mf = scf.RHF(mol).density_fit().x2c() # Stream style
energy = mf.kernel()
print('E = %.12f, ref = -76.075408156180' % energy)
#
# 3. The order to apply X2C or newton method matters. If relativistic effects
# Adjust the MPI schedular and scratch directory if needed. # NOTE the DMRG-NEVPT2 is expensive, it requires about 8 GB memory per processor # #from pyscf.dmrgscf import settings #settings.MPIPREFIX = 'srun' #settings.BLOCKSCRATCHDIR = '/scratch' from pyscf.dmrgscf import DMRGCI, DMRGSCF from pyscf import mrpt # # Redirect output to another file # mol.build(verbose=7, output='hs_dmrg.out') mf = scf.sfx2c1e(scf.RHF(mol)) mc = DMRGSCF(mf, norb, [nalpha, nbeta]) mc.chkfile = 'hs_mc.chk' mc.max_memory = 30000 mc.fcisolver.maxM = 1000 mc.fcisolver.tol = 1e-6 orbs = mc.sort_mo(caslst, coeff, base=0) mc.mc1step(orbs) # # CASCI-NEVPT2 # # If DMRG-CASSCF was finished without any problems (eg convergence, wall time # limits on cluster etc), one can simply continue with DMRG-NEVPT2 # mrpt.NEVPT(mc).kernel() #
# NEVPT2 calculation requires about 200 GB memory in total
#
b = 1.5
mol = gto.Mole()
mol.verbose = 5
mol.output = 'cr2-%3.2f.out' % b
mol.atom = [
['Cr',( 0.000000, 0.000000, -b/2)],
['Cr',( 0.000000, 0.000000, b/2)],
]
mol.basis = {'Cr': 'ccpvdz-dk'}
mol.symmetry = True
mol.build()
m = scf.sfx2c1e(scf.RHF(mol)).run(conv_tol=1e-9, chkfile='hf_chk-%s'%b, level_shift=0.5)
#
# Note: stream operations are used here. This one line code is equivalent to
# the following serial statements.
#
#m = scf.sfx2c1e(scf.RHF(mol))
#m.conv_tol = 1e-9
#m.chkfile = 'hf_chk-%s'%b
#m.level_shift = 0.5
#m.kernel()
dm = m.make_rdm1()
m.level_shift = 0
m.scf(dm)
mc = DMRGSCF(m, 20, 28) # 20o, 28e
def test_init(self):
from pyscf import dft
from pyscf import x2c
mol_r = mol
mol_u = gto.M(atom='Li', spin=1, verbose=0)
mol_r1 = gto.M(atom='H', spin=1, verbose=0)
sym_mol_r = molsym
sym_mol_u = gto.M(atom='Li', spin=1, symmetry=1, verbose=0)
sym_mol_r1 = gto.M(atom='H', spin=1, symmetry=1, verbose=0)
self.assertTrue(isinstance(scf.RKS(mol_r), dft.rks.RKS))
self.assertTrue(isinstance(scf.RKS(mol_u), dft.roks.ROKS))
self.assertTrue(isinstance(scf.UKS(mol_r), dft.uks.UKS))
self.assertTrue(isinstance(scf.ROKS(mol_r), dft.roks.ROKS))
self.assertTrue(isinstance(scf.GKS(mol_r), dft.gks.GKS))
self.assertTrue(isinstance(scf.KS(mol_r), dft.rks.RKS))
self.assertTrue(isinstance(scf.KS(mol_u), dft.uks.UKS))
self.assertTrue(isinstance(scf.RHF(mol_r), scf.hf.RHF))
self.assertTrue(isinstance(scf.RHF(mol_u), scf.rohf.ROHF))
self.assertTrue(isinstance(scf.RHF(mol_r1), scf.rohf.ROHF))
self.assertTrue(isinstance(scf.UHF(mol_r), scf.uhf.UHF))
self.assertTrue(isinstance(scf.UHF(mol_u), scf.uhf.UHF))
self.assertTrue(isinstance(scf.UHF(mol_r1), scf.uhf.UHF))
self.assertTrue(isinstance(scf.ROHF(mol_r), scf.rohf.ROHF))
self.assertTrue(isinstance(scf.ROHF(mol_u), scf.rohf.ROHF))
self.assertTrue(isinstance(scf.ROHF(mol_r1), scf.rohf.ROHF))
self.assertTrue(isinstance(scf.HF(mol_r), scf.hf.RHF))
self.assertTrue(isinstance(scf.HF(mol_u), scf.uhf.UHF))
self.assertTrue(isinstance(scf.HF(mol_r1), scf.rohf.ROHF))
self.assertTrue(isinstance(scf.GHF(mol_r), scf.ghf.GHF))
self.assertTrue(isinstance(scf.GHF(mol_u), scf.ghf.GHF))
self.assertTrue(isinstance(scf.GHF(mol_r1), scf.ghf.GHF))
self.assertTrue(not isinstance(scf.DHF(mol_r), scf.dhf.RHF))
self.assertTrue(isinstance(scf.DHF(mol_u), scf.dhf.UHF))
self.assertTrue(isinstance(scf.DHF(mol_r1), scf.dhf.HF1e))
self.assertTrue(isinstance(scf.RHF(sym_mol_r), scf.hf_symm.RHF))
self.assertTrue(isinstance(scf.RHF(sym_mol_u), scf.hf_symm.ROHF))
self.assertTrue(isinstance(scf.RHF(sym_mol_r1), scf.hf_symm.ROHF))
self.assertTrue(isinstance(scf.UHF(sym_mol_r), scf.uhf_symm.UHF))
self.assertTrue(isinstance(scf.UHF(sym_mol_u), scf.uhf_symm.UHF))
self.assertTrue(isinstance(scf.UHF(sym_mol_r1), scf.uhf_symm.UHF))
self.assertTrue(isinstance(scf.ROHF(sym_mol_r), scf.hf_symm.ROHF))
self.assertTrue(isinstance(scf.ROHF(sym_mol_u), scf.hf_symm.ROHF))
self.assertTrue(isinstance(scf.ROHF(sym_mol_r1), scf.hf_symm.ROHF))
self.assertTrue(isinstance(scf.HF(sym_mol_r), scf.hf_symm.RHF))
self.assertTrue(isinstance(scf.HF(sym_mol_u), scf.uhf_symm.UHF))
self.assertTrue(isinstance(scf.HF(sym_mol_r1), scf.hf_symm.ROHF))
self.assertTrue(isinstance(scf.GHF(sym_mol_r), scf.ghf_symm.GHF))
self.assertTrue(isinstance(scf.GHF(sym_mol_u), scf.ghf_symm.GHF))
self.assertTrue(isinstance(scf.GHF(sym_mol_r1), scf.ghf_symm.GHF))
self.assertTrue(isinstance(scf.X2C(mol_r), x2c.x2c.UHF))
self.assertTrue(isinstance(scf.sfx2c1e(scf.HF(mol_r)), scf.rhf.RHF))
self.assertTrue(isinstance(scf.sfx2c1e(scf.HF(mol_u)), scf.uhf.UHF))
self.assertTrue(isinstance(scf.sfx2c1e(scf.HF(mol_r1)), scf.rohf.ROHF))
self.assertTrue(isinstance(scf.sfx2c1e(scf.HF(sym_mol_r)), scf.rhf_symm.RHF))
self.assertTrue(isinstance(scf.sfx2c1e(scf.HF(sym_mol_u)), scf.uhf_symm.UHF))
self.assertTrue(isinstance(scf.sfx2c1e(scf.HF(sym_mol_r1)), scf.hf_symm.ROHF))
self.assertTrue(isinstance(scf.density_fit(scf.HF(mol_r)), scf.rhf.RHF))
self.assertTrue(isinstance(scf.density_fit(scf.HF(mol_u)), scf.uhf.UHF))
self.assertTrue(isinstance(scf.density_fit(scf.HF(mol_r1)), scf.rohf.ROHF))
self.assertTrue(isinstance(scf.density_fit(scf.HF(sym_mol_r)), scf.rhf_symm.RHF))
self.assertTrue(isinstance(scf.density_fit(scf.HF(sym_mol_u)), scf.uhf_symm.UHF))
self.assertTrue(isinstance(scf.density_fit(scf.HF(sym_mol_r1)), scf.hf_symm.ROHF))
self.assertTrue(isinstance(scf.newton(scf.HF(mol_r)), scf.rhf.RHF))
self.assertTrue(isinstance(scf.newton(scf.HF(mol_u)), scf.uhf.UHF))
self.assertTrue(isinstance(scf.newton(scf.HF(mol_r1)), scf.rohf.ROHF))
self.assertTrue(isinstance(scf.newton(scf.HF(sym_mol_r)), scf.rhf_symm.RHF))
self.assertTrue(isinstance(scf.newton(scf.HF(sym_mol_u)), scf.uhf_symm.UHF))
self.assertTrue(isinstance(scf.newton(scf.HF(sym_mol_r1)), scf.hf_symm.ROHF))
mf = scf.RHF(mol)
mf.irrep_nelec = {'Ag': (6, 3), 'B1g': (1, 0), 'B2g': (1, 0), 'B3g': (1, 0)}
mf.scf(rdm1)
#
# The third way to force the calculation strictly following the correct
# configurations is the second order SCF optimizaiton. In the following code,
# we call a calculation on cation for a correct HF configuration with spherical
# symmetry. This HF configuration is next pass to second order SCF solver
# scf.newton to solve X2C-ROHF model of the open shell atom.
#
mol = gto.M(verbose=4,
symmetry=True,
atom=[
['Cr', (0, 0, 0)],
],
basis='cc-pvdz-dk',
charge=6,
spin=0)
mf = scf.sfx2c1e(scf.RHF(mol)).run()
mo, mo_occ = mf.mo_coeff, mf.mo_occ
mol.charge = 0
mol.spin = 6
mol.build(False, False)
mf = scf.newton(scf.sfx2c1e(scf.RHF(mol)))
mo_occ[9:15] = 1
mf.kernel(mo, mo_occ)
#mf.analyze()
the Hessian for the large-basis-density-fitted-scf scheme.
'''
mol = gto.Mole()
mol.build(
verbose=0,
atom='''8 0 0. 0
1 0 -0.757 0.587
1 0 0.757 0.587''',
basis='ccpvdz',
)
#
# 1. spin-free X2C-HF with density fitting approximation on 2E integrals
#
mf = scf.density_fit(scf.sfx2c1e(scf.RHF(mol)))
mf = scf.RHF(mol).x2c().density_fit() # Stream style
energy = mf.kernel()
print('E = %.12f, ref = -76.075408156180' % energy)
#
# 2. spin-free X2C correction for density-fitting HF. Since X2C correction is
# commutable with density fitting operation, it is fully equivalent to case 1.
#
mf = scf.sfx2c1e(scf.density_fit(scf.RHF(mol)))
mf = scf.RHF(mol).density_fit().x2c() # Stream style
energy = mf.kernel()
print('E = %.12f, ref = -76.075408156180' % energy)
#
# 3. The order to apply X2C or newton method matters. If relativistic effects
def run(b, dm_guess, mo_guess, ci=None):
mol = gto.Mole()
mol.verbose = 5
mol.output = 'cr2-%3.2f.out' % b
mol.atom = [
['Cr', (0., 0., -b / 2)],
['Cr', (0., 0., b / 2)],
]
mol.basis = 'ccpvdzdk'
mol.symmetry = True
mol.build()
mf = scf.sfx2c1e(scf.RHF(mol))
mf.max_cycle = 100
mf.conv_tol = 1e-9
mf.kernel(dm_guess)
#---------------------
# CAS(12,12)
#
# The active space of CAS(12,42) can be generated by function sort_mo_by_irrep,
# or AVAS, dmet_cas methods. Here we first run a CAS(12,12) calculation and
# using the lowest CASSCF canonicalized orbitals in the CAS(12,42) calculation
# as the core and valence orbitals.
mc = mcscf.CASSCF(mf, 12, 12)
if mo_guess is None:
# the initial guess for first calculation
ncas = {
'A1g': 2,
'E1gx': 1,
'E1gy': 1,
'E2gx': 1,
'E2gy': 1,
'A1u': 2,
'E1ux': 1,
'E1uy': 1,
'E2ux': 1,
'E2uy': 1
}
mo_guess = mcscf.sort_mo_by_irrep(mc, mf.mo_coeff, ncas, ncore)
else:
mo_guess = mcscf.project_init_guess(mc, mo_guess)
# Projection may destroy the spatial symmetry of the MCSCF orbitals.
try:
print(
'Irreps of the projected CAS(12,12) orbitals',
symm.label_orb_symm(mol, mol.irrep_id, mol.symm_orb, mo_guess))
except:
print('Projected CAS(12,12) orbitals does not have right symmetry')
# FCI solver with multi-threads is not stable enough for this sytem
mc.fcisolver.threads = 1
# To avoid spin contamination
mc.fix_spin_()
# By default, canonicalization as well as the CASSCF optimization do not
# change the orbital symmetry labels. "Orbital energy" mc.mo_energy, the
# diagonal elements of the general fock matrix, may have wrong ordering.
# To use the lowest CASSCF orbitals as the core + active orbitals in the next
# step, we have to sort the orbitals based on the "orbital energy". This
# operation will change the orbital symmetry labels.
mc.sorting_mo_energy = True
# "mc.natorb = True" will transform the active space, to its natural orbital
# representation. By default, the active space orbitals are NOT reordered
# even the option sorting_mo_energy is enabled. Transforming the active space
# orbitals is a dangerous operation because it needs also to update the CI
# wavefunction. For DMRG solver (or other approximate FCI solver), the CI
# wavefunction may not be able to consistently converged and it leads to
# inconsistency between the orbital space and the CI wavefunction
# representations. Unless required by the following CAS calculation, setting
# mc.natorb=True should be avoided
# mc.natorb = True
mc.kernel(mo_guess, ci)
mc.analyze()
#---------------------
# CAS(12,42)
#
# Using the lowest CASSCF canonicalized orbitals in the CAS(12,42) DMRG-CASSCF
# calculation.
norb = 42
nelec = 12
mc1 = DMRGSCF(mf, norb, nelec)
mc1.fcisolver.maxM = 4000
# Enable internal rotation since the bond dimension of DMRG calculation is
# small, the active space energy can be optimized wrt to the orbital rotation
# within the active space.
mc1.internal_rotation = True
# Sorting the orbital energy is not a step of must here.
# mc1.sorting_mo_energy = True
# mc1.natorb = True
mc1.kernel()
# Passing the results as an initial guess to the next point.
return mf.make_rdm1(), mc.mo_coeff, mc.ci