def test_ORD_RPA_singlet_BC2H4_cation_HF_STO3G():
ref = BC2H4_cation_HF_STO3G_RPA_singlet_nwchem
pyscfmol = molecules.molecule_bc2h4_cation_sto3g()
pyscfmol.build()
mf = pyscf.scf.RHF(pyscfmol)
mf.scf()
C = utils.fix_mocoeffs_shape(mf.mo_coeff)
E = utils.fix_moenergies_shape(mf.mo_energy)
occupations = occupations_from_pyscf_mol(pyscfmol, C)
frequencies = [0.0, 0.001, 0.0773178, 0.128347]
ord_solver = optrot.ORD(
Program.PySCF,
pyscfmol,
cphf.CPHF(solvers.ExactInv(C, E, occupations)),
C,
E,
occupations,
frequencies=frequencies,
do_dipvel=False,
)
ord_solver.form_operators()
ord_solver.run(hamiltonian=Hamiltonian.RPA, spin=Spin.singlet)
ord_solver.form_results()
print("Polarizabilities")
assert len(frequencies) == len(ord_solver.polarizabilities)
thresh = 5.0e-4
for idxf, frequency in enumerate(frequencies):
ref_polar = ref[frequency]["polar"]
res_polar = ord_solver.polarizabilities[idxf]
abs_diff = abs(res_polar - ref_polar)
print(idxf, frequency)
print(res_polar)
print(abs_diff)
assert (abs_diff < thresh).all()
print(r"\beta(\omega)")
thresh = 5.0e-2
for idxf, frequency in enumerate(frequencies):
if "orbeta" in ref[frequency]:
ref_beta = ref[frequency]["orbeta"]
# TODO why no speed of light?
# TODO why the (1/2)?
res_beta = -(0.5 /
frequency) * ord_solver.driver.results[idxf][3:6, 0:3]
abs_diff = abs(res_beta - ref_beta)
print(idxf, frequency)
print(res_beta)
print(abs_diff)
assert (abs_diff < thresh).all()
def test_ECD_RPA_singlet_BC2H4_cation_HF_STO3G() -> None:
ref = BC2H4_cation_HF_STO3G_RPA_singlet_nwchem
nroots = ref["nroots"]
mol = molecules.molecule_bc2h4_cation_sto3g()
mol.build()
mf = pyscf.scf.RHF(mol)
mf.scf()
C = utils.fix_mocoeffs_shape(mf.mo_coeff)
E = utils.fix_moenergies_shape(mf.mo_energy)
occupations = occupations_from_pyscf_mol(mol, C)
ecd_dipvel_rpa = ecd.ECD(
Program.PySCF,
mol,
td.TDHF(solvers.ExactDiagonalizationSolver(C, E, occupations)),
C,
E,
occupations,
do_dipvel=True,
)
ecd_dipvel_rpa.form_operators()
ecd_dipvel_rpa.run(hamiltonian=Hamiltonian.RPA, spin=Spin.singlet)
ecd_dipvel_rpa.form_results()
print("excitation energies")
ref_etenergies = np.array(ref["etenergies"])
res_etenergies = ecd_dipvel_rpa.driver.solver.eigvals.real[:nroots]
print("ref, res")
for refval, resval in zip(ref_etenergies, res_etenergies):
print(refval, resval)
thresh = 2.5e-7
for i in range(nroots):
abs_diff = abs(ref_etenergies[i] - res_etenergies[i])
assert abs_diff < thresh
print("dipole (length) oscillator strengths")
ref_etoscslen = np.array(ref["etoscslen"])
res_etoscslen = ecd_dipvel_rpa.driver.solver.operators[
1].total_oscillator_strengths[:nroots]
print("ref, res")
for refval, resval in zip(ref_etoscslen, res_etoscslen):
print(refval, resval)
thresh = 1.0e-5
for i in range(nroots):
abs_diff = abs(ref_etoscslen[i] - res_etoscslen[i])
assert abs_diff < thresh
# TODO
print("TODO dipole (mixed length/velocity) oscillator strengths")
# TODO
print("TODO dipole (velocity) oscillator strengths")
ref_etoscsvel = np.array(ref["etoscsvel"])
res_etoscsvel = ecd_dipvel_rpa.driver.solver.operators[
2].total_oscillator_strengths[:nroots]
# print('ref, res')
# for refval, resval in zip(ref_etoscsvel, res_etoscsvel):
# print(refval, resval)
# print(ref_etoscsvel / res_etoscsvel)
# print(res_etoscsvel / ref_etoscsvel)
print("rotatory strengths (length)")
ref_etrotstrlen = np.array(ref["etrotstrlen"])
res_etrotstrlen = ecd_dipvel_rpa.rotational_strengths_diplen[:nroots]
print("ref, res")
for refval, resval in zip(ref_etrotstrlen, res_etrotstrlen):
print(refval, resval)
# TODO unlike other quantities, the error isn't uniformly
# distributed among the roots; how should this be handled?
thresh = 1.5e1
for i in range(nroots):
abs_diff = abs(ref_etrotstrlen[i] - res_etrotstrlen[i])
assert abs_diff < thresh
print("rotatory strengths (velocity)")
ref_etrotstrvel = np.array(ref["etrotstrvel"])
res_etrotstrvel = ecd_dipvel_rpa.rotational_strengths_dipvel[:nroots]
print("ref, res")
for refval, resval in zip(ref_etrotstrvel, res_etrotstrvel):
print(refval, resval)
thresh = 1.0e-2
for i in range(nroots):
abs_diff = abs(ref_etrotstrvel[i] - res_etrotstrvel[i])
assert abs_diff < thresh
def test_ECD_RPA_singlet_BC2H4_cation_HF_STO3G():
ref = BC2H4_cation_HF_STO3G_RPA_singlet_nwchem
nroots = ref["nroots"]
mol = molecules.molecule_bc2h4_cation_sto3g()
mol.build()
mf = pyscf.scf.RHF(mol)
mf.scf()
C = utils.fix_mocoeffs_shape(mf.mo_coeff)
E = utils.fix_moenergies_shape(mf.mo_energy)
occupations = utils.occupations_from_pyscf_mol(mol, C)
ecd_dipvel_rpa = ecd.ECD(Program.PySCF, mol, C, E, occupations, do_dipvel=True)
ecd_dipvel_rpa.form_operators()
ecd_dipvel_rpa.run(hamiltonian="rpa", spin="singlet")
ecd_dipvel_rpa.form_results()
print("excitation energies")
ref_etenergies = np.array(ref["etenergies"])
res_etenergies = ecd_dipvel_rpa.driver.solver.eigvals.real[:nroots]
print("ref, res")
for refval, resval in zip(ref_etenergies, res_etenergies):
print(refval, resval)
thresh = 1.0e-7
for i in range(nroots):
abs_diff = abs(ref_etenergies[i] - res_etenergies[i])
assert abs_diff < thresh
print("dipole (length) oscillator strengths")
ref_etoscslen = np.array(ref["etoscslen"])
res_etoscslen = ecd_dipvel_rpa.driver.solver.operators[1].total_oscillator_strengths[
:nroots
]
print("ref, res")
for refval, resval in zip(ref_etoscslen, res_etoscslen):
print(refval, resval)
thresh = 1.0e-5
for i in range(nroots):
abs_diff = abs(ref_etoscslen[i] - res_etoscslen[i])
assert abs_diff < thresh
# TODO
print("TODO dipole (mixed length/velocity) oscillator strengths")
# TODO
print("TODO dipole (velocity) oscillator strengths")
ref_etoscsvel = np.array(ref["etoscsvel"])
res_etoscsvel = ecd_dipvel_rpa.driver.solver.operators[2].total_oscillator_strengths[
:nroots
]
# print('ref, res')
# for refval, resval in zip(ref_etoscsvel, res_etoscsvel):
# print(refval, resval)
# print(ref_etoscsvel / res_etoscsvel)
# print(res_etoscsvel / ref_etoscsvel)
print("rotatory strengths (length)")
ref_etrotstrlen = np.array(ref["etrotstrlen"])
res_etrotstrlen = ecd_dipvel_rpa.rotational_strengths_diplen[:nroots]
print("ref, res")
for refval, resval in zip(ref_etrotstrlen, res_etrotstrlen):
print(refval, resval)
# TODO unlike other quantities, the error isn't uniformly
# distributed among the roots; how should this be handled?
thresh = 1.5e1
for i in range(nroots):
abs_diff = abs(ref_etrotstrlen[i] - res_etrotstrlen[i])
assert abs_diff < thresh
print("rotatory strengths (velocity)")
ref_etrotstrvel = np.array(ref["etrotstrvel"])
res_etrotstrvel = ecd_dipvel_rpa.rotational_strengths_dipvel[:nroots]
print("ref, res")
for refval, resval in zip(ref_etrotstrvel, res_etrotstrvel):
print(refval, resval)
thresh = 1.0e-2
for i in range(nroots):
abs_diff = abs(ref_etrotstrvel[i] - res_etrotstrvel[i])
assert abs_diff < thresh
# with open(os.path.join(refdir, 'BC2H4_cation', 'nwchem_singlet_rpa_velocity_root.str')) as fh:
# ref_str = fh.read()
# res_str = ecd_dipvel_rpa.print_results_nwchem()
# assert res_str == ref_str
# print(ecd_dipvel_rpa.print_results_nwchem())
# print(ecd_dipvel_rpa.print_results_orca())
# print(ecd_dipvel_rpa.print_results_qchem())
# tmom_diplen = ecd_dipvel_rpa.driver.solver.operators[1].transition_moments
# tmom_dipvel = ecd_dipvel_rpa.driver.solver.operators[2].transition_moments
# print(tmom_diplen)
# print('dipole')
# for i in range(nroots):
# print((2 / 3) * res_etenergies[i] * np.dot(tmom_diplen[i], tmom_diplen[i]))
# print('mixed')
# for i in range(nroots):
# print((2 / 3) * res_etenergies[i] * np.dot(tmom_diplen[i], tmom_dipvel[i]))
# print('sum rule')
# print('ref_etoscslen:', sum(ref_etoscslen))
# print('res_etoscslen:', sum(res_etoscslen))
# # print('ref_etoscsmix:', sum(ref_etoscsmix))
# # print('res_etoscsmix:', sum(res_etoscsmix))
# print('ref_etoscsvel:', sum(ref_etoscsvel))
# print('res_etoscsvel:', sum(res_etoscsvel))
return
def test_ECD_TDA_singlet_BC2H4_cation_HF_STO3G():
ref = BC2H4_cation_HF_STO3G_TDA_singlet_orca
nroots = ref["nroots"]
mol = molecules.molecule_bc2h4_cation_sto3g()
mol.build()
mf = pyscf.scf.RHF(mol)
mf.scf()
C = utils.fix_mocoeffs_shape(mf.mo_coeff)
E = utils.fix_moenergies_shape(mf.mo_energy)
occupations = utils.occupations_from_pyscf_mol(mol, C)
ecd_dipvel_tda = ecd.ECD(Program.PySCF, mol, C, E, occupations, do_dipvel=True)
ecd_dipvel_tda.form_operators()
ecd_dipvel_tda.run(hamiltonian="tda", spin="singlet")
ecd_dipvel_tda.form_results()
print("excitation energies")
ref_etenergies = np.array(ref["etenergies"])
res_etenergies = ecd_dipvel_tda.driver.solver.eigvals.real[:nroots]
print("ref, res")
for refval, resval in zip(ref_etenergies, res_etenergies):
print(refval, resval)
# TODO this might be from ORCA, should use NWChem instead
thresh = 1.0e-3
for i in range(nroots):
abs_diff = abs(ref_etenergies[i] - res_etenergies[i])
assert abs_diff < thresh
print("dipole (length) oscillator strengths")
ref_etoscslen = np.array(ref["etoscslen"])
res_etoscslen = ecd_dipvel_tda.driver.solver.operators[1].total_oscillator_strengths[
:nroots
]
print("ref, res")
for refval, resval in zip(ref_etoscslen, res_etoscslen):
print(refval, resval)
thresh = 1.0e-3
# np.testing.assert_allclose(ref_etoscslen, res_etoscslen)
for i in range(nroots):
abs_diff = abs(ref_etoscslen[i] - res_etoscslen[i])
assert abs_diff < thresh
# TODO
print("TODO dipole (mixed length/velocity) oscillator strengths")
# TODO
print("TODO dipole (velocity) oscillator strengths")
print("rotatory strengths (length)")
ref_etrotstrlen = np.array(ref["etrotstrlen"])
res_etrotstrlen = ecd_dipvel_tda.rotational_strengths_diplen[:nroots]
print("ref, res")
for refval, resval in zip(ref_etrotstrlen, res_etrotstrlen):
print(refval, resval)
# TODO unlike other quantities, the error isn't uniformly
# distributed among the roots; how should this be handled?
thresh = 1.0e2
for i in range(nroots):
abs_diff = abs(ref_etrotstrlen[i] - res_etrotstrlen[i])
assert abs_diff < thresh
# print('rotatory strengths (velocity)')
# ref_etrotstrvel = np.array(ref['etrotstrvel'])
# res_etrotstrvel = ecd_dipvel_tda.rotational_strengths_dipvel[:nroots]
# print('ref, res')
# for refval, resval in zip(ref_etrotstrvel, res_etrotstrvel):
# print(refval, resval)
# thresh = 1.0e-2
# for i in range(nroots):
# abs_diff = abs(ref_etrotstrvel[i] - res_etrotstrvel[i])
# assert abs_diff < thresh
# print(ecd_dipvel_tda.print_results_nwchem())
# print(ecd_dipvel_tda.print_results_orca())
# print(ecd_dipvel_tda.print_results_qchem())
return
def test_ORD_RPA_singlet_BC2H4_cation_HF_STO3G():
ref = BC2H4_cation_HF_STO3G_RPA_singlet_nwchem
pyscfmol = molecules.molecule_bc2h4_cation_sto3g()
pyscfmol.build()
mf = pyscf.scf.RHF(pyscfmol)
mf.scf()
C = utils.fix_mocoeffs_shape(mf.mo_coeff)
E = utils.fix_moenergies_shape(mf.mo_energy)
occupations = utils.occupations_from_pyscf_mol(pyscfmol, C)
frequencies = [0.0, 0.001, 0.0773178, 0.128347]
ord_solver = optrot.ORD(
Program.PySCF,
pyscfmol,
C,
E,
occupations,
frequencies=frequencies,
do_dipvel=False,
)
ord_solver.form_operators()
ord_solver.run(hamiltonian="rpa", spin="singlet")
ord_solver.form_results()
print("Polarizabilities")
assert len(frequencies) == len(ord_solver.polarizabilities)
thresh = 5.0e-4
for idxf, frequency in enumerate(frequencies):
ref_polar = ref[frequency]["polar"]
res_polar = ord_solver.polarizabilities[idxf]
abs_diff = abs(res_polar - ref_polar)
print(idxf, frequency)
print(res_polar)
print(abs_diff)
assert (abs_diff < thresh).all()
print(r"\beta(\omega)")
thresh = 5.0e-2
for idxf, frequency in enumerate(frequencies):
if "orbeta" in ref[frequency]:
ref_beta = ref[frequency]["orbeta"]
# TODO why no speed of light?
# TODO why the (1/2)?
res_beta = -(0.5 / frequency) * ord_solver.driver.results[idxf][3:6, 0:3]
abs_diff = abs(res_beta - ref_beta)
print(idxf, frequency)
print(res_beta)
print(abs_diff)
assert (abs_diff < thresh).all()
# from ecd import ECD
# ecd = ECD(pyscfmol, C, E, occupations, do_dipvel=True, do_tda=False)
# ecd.run()
# ecd.form_results()
# ord_solver.form_operators()
# ord_solver.run()
# ord_solver.form_results()
# from constants import esuecd
# prefac = -(2 / 3) / esuecd
# for idxf, frequency in enumerate(frequencies):
# print(sum(prefac * ecd.rotational_strengths_diplen / ((frequency ** 2) * (ecd.solver.eigvals.real ** 2))))
return