def test_ao2mo_hand_against_pyscf_rhf_partial():
mol = molecules_pyscf.molecule_physicists_water_sto3g()
mol.build()
mf = pyscf.scf.RHF(mol)
mf.kernel()
C = fix_mocoeffs_shape(mf.mo_coeff)
occupations = occupations_from_pyscf_mol(mol, C)
nocc, nvirt, _, _ = occupations
nmo = nocc + nvirt
ntransforms = 2
o = slice(0, nocc)
v = slice(nocc, nmo)
ao2mo = AO2MOpyscf(C, verbose=mol.verbose, pyscfmol=mol)
ao2mo.perform_rhf_partial()
assert len(ao2mo.tei_mo) == ntransforms
tei_mo_ovov_pyscf = ao2mo.tei_mo[0]
tei_mo_oovv_pyscf = ao2mo.tei_mo[1]
tei_ao = mol.intor("int2e_sph", aosym="s1")
print("1. Use the class method explicitly.")
tei_mo_ovov_hand = AO2MO.transform(
tei_ao, C[0, :, o], C[0, :, v], C[0, :, o], C[0, :, v]
)
tei_mo_oovv_hand = AO2MO.transform(
tei_ao, C[0, :, o], C[0, :, o], C[0, :, v], C[0, :, v]
)
assert tei_mo_ovov_pyscf.shape == tei_mo_ovov_hand.shape == (nocc, nvirt, nocc, nvirt)
assert tei_mo_oovv_pyscf.shape == tei_mo_oovv_hand.shape == (nocc, nocc, nvirt, nvirt)
np.testing.assert_allclose(tei_mo_ovov_hand, tei_mo_ovov_pyscf, rtol=0, atol=1.0e-15)
np.testing.assert_allclose(tei_mo_oovv_hand, tei_mo_oovv_pyscf, rtol=0, atol=1.0e-15)
print("2. Use the class method normally.")
ao2mo_method = AO2MO(C, occupations, verbose=mol.verbose, I=tei_ao)
ao2mo_method.perform_rhf_partial()
assert len(ao2mo_method.tei_mo) == ntransforms
tei_mo_ovov_method = ao2mo_method.tei_mo[0]
tei_mo_oovv_method = ao2mo_method.tei_mo[1]
assert (
tei_mo_ovov_pyscf.shape == tei_mo_ovov_method.shape == (nocc, nvirt, nocc, nvirt)
)
assert (
tei_mo_oovv_pyscf.shape == tei_mo_oovv_method.shape == (nocc, nocc, nvirt, nvirt)
)
np.testing.assert_allclose(
tei_mo_ovov_method, tei_mo_ovov_pyscf, rtol=0, atol=1.0e-15
)
np.testing.assert_allclose(
tei_mo_oovv_method, tei_mo_oovv_pyscf, rtol=0, atol=1.0e-15
)
return
def form_tei_mo(
self, program: Program, program_obj, tei_mo_type: AO2MOTransformationType
) -> None:
assert isinstance(program, Program)
# TODO program_obj
assert isinstance(tei_mo_type, AO2MOTransformationType)
nden = self.mocoeffs.shape[0]
assert nden in (1, 2)
if program == Program.PySCF:
from pyresponse.pyscf.ao2mo import AO2MOpyscf
ao2mo = AO2MOpyscf(self.mocoeffs, program_obj.verbose, program_obj)
elif program == Program.Psi4:
import psi4
from pyresponse.ao2mo import AO2MO
assert isinstance(program_obj, psi4.core.Molecule)
ao2mo = AO2MO(
self.mocoeffs,
self.occupations,
I=psi4.core.MintsHelper(
psi4.core.Wavefunction.build(
program_obj, psi4.core.get_global_option("BASIS")
).basisset()
)
.ao_eri()
.np,
)
else:
raise RuntimeError
if tei_mo_type == AO2MOTransformationType.partial and nden == 2:
ao2mo.perform_uhf_partial()
elif tei_mo_type == AO2MOTransformationType.partial and nden == 1:
ao2mo.perform_rhf_partial()
elif tei_mo_type == AO2MOTransformationType.full and nden == 2:
ao2mo.perform_uhf_full()
elif tei_mo_type == AO2MOTransformationType.full and nden == 1:
ao2mo.perform_rhf_full()
else:
raise ValueError(f"Unknown combination of tei_mo_type {tei_mo_type} and nden {nden}")
self.tei_mo = ao2mo.tei_mo
self.tei_mo_type = tei_mo_type
def form_tei_mo(self, program, program_obj, tei_mo_type="partial"):
assert tei_mo_type in ("partial", "full")
nden = self.mocoeffs.shape[0]
assert nden in (1, 2)
if program == Program.PySCF:
from pyresponse.pyscf.ao2mo import AO2MOpyscf
ao2mo = AO2MOpyscf(self.mocoeffs, program_obj.verbose, program_obj)
elif program == Program.Psi4:
from pyresponse.ao2mo import AO2MO
import psi4
assert isinstance(program_obj, psi4.core.Molecule)
ao2mo = AO2MO(
self.mocoeffs,
self.occupations,
I=psi4.core.MintsHelper(
psi4.core.Wavefunction.build(
program_obj, psi4.core.get_global_option(
"BASIS")).basisset()).ao_eri().np,
)
else:
raise RuntimeError
if tei_mo_type == "partial" and nden == 2:
ao2mo.perform_uhf_partial()
elif tei_mo_type == "partial" and nden == 1:
ao2mo.perform_rhf_partial()
elif tei_mo_type == "full" and nden == 2:
ao2mo.perform_uhf_full()
elif tei_mo_type == "full" and nden == 1:
ao2mo.perform_rhf_full()
else:
# TODO more specific exception
raise Exception
self.tei_mo = ao2mo.tei_mo
self.tei_mo_type = tei_mo_type
def test_atomic_polar_tensor_rhf():
mol = molecules.molecule_physicists_water_sto3g()
mol.reset_point_group("c1")
mol.update_geometry()
psi4.core.set_active_molecule(mol)
options = {
"BASIS": "STO-3G",
"SCF_TYPE": "PK",
"E_CONVERGENCE": 1e-10,
"D_CONVERGENCE": 1e-10,
}
psi4.set_options(options)
_, wfn = psi4.energy("hf", return_wfn=True)
mints = psi4.core.MintsHelper(wfn)
C = mocoeffs_from_psi4wfn(wfn)
E = moenergies_from_psi4wfn(wfn)
occupations = occupations_from_psi4wfn(wfn)
nocc, nvir, _, _ = occupations
norb = nocc + nvir
# electric perturbation part
ao2mo = AO2MO(C, occupations, I=np.asarray(mints.ao_eri()))
ao2mo.perform_rhf_full()
solver = ExactInv(C, E, occupations)
solver.tei_mo = ao2mo.tei_mo
solver.tei_mo_type = "full"
driver = CPHF(solver)
operator_diplen = Operator(label="dipole",
is_imaginary=False,
is_spin_dependent=False,
triplet=False)
# integrals_diplen_ao = self.pyscfmol.intor('cint1e_r_sph', comp=3)
M = np.stack([np.asarray(Mc) for Mc in mints.ao_dipole()])
operator_diplen.ao_integrals = M
driver.add_operator(operator_diplen)
# geometric perturbation part
operator_geometric = Operator(label="nuclear",
is_imaginary=False,
is_spin_dependent=False,
triplet=False)
operator_geometric.form_rhs_geometric(C, occupations, mol.natom(),
solver.tei_mo[0], mints)
print(operator_geometric.label)
print(operator_geometric.mo_integrals_ai_alph)
print(operator_diplen.label)
print(operator_diplen.mo_integrals_ai_alph)
# hack for dim check in solver
operator_geometric.ao_integrals = np.zeros(
(3 * mol.natom(), M.shape[1], M.shape[2]))
# bypass driver's call to form_rhs
driver.solver.operators.append(operator_geometric)
driver.run()
print(driver.results[0])
print(driver.results[0].T)
print(driver.results[0] - driver.results[0].T)
print(operator_geometric.rspvecs_alph[0])
# Nuclear contribution to dipole gradient
# Electronic contributions to static part of dipole gradient
# Reorthonormalization part of dipole gradient
# Static contribution to dipole gradient
# Relaxation part of dipole gradient
# Total dipole gradient - TRAROT
print("Nuclear contribution to dipole gradient")
natom = mol.natom()
Z = np.asarray([mol.Z(i) for i in range(natom)])
nuclear_contrib = np.concatenate(
[np.diag(Z.take(3 * [i])) for i in range(natom)])
print(nuclear_contrib)
return locals()