def test_guess_mix_for_broken_symmetry(inp):
refENuc = 0.17639240356
refSCF = -0.82648407827446
refBSSCF = -0.99872135103903
h2 = psi4.geometry("""
0 1
H
H 1 3.0
symmetry c1
""")
psi4.set_options({
"reference": "uhf",
"e_convergence": 12,
"basis": "cc-pvdz"
})
psi4.set_options(inp.get("options", {}))
thisSCF = psi4.energy("scf")
psi4.set_options(inp.get("late_options", {}))
psi4.set_options({"guess_mix": True})
thisBSSCF = psi4.energy("scf")
assert compare_values(refENuc, h2.nuclear_repulsion_energy(), 10,
"Nuclear repulsion energy")
assert compare_values(refSCF, thisSCF, 10, "Reference energy")
assert compare_values(refBSSCF, thisBSSCF, 10,
"Reference broken-symmetry energy")
def test_schwarz_vs_density_energy():
"""Checks difference in Hartree-Fock energy between Schwarz and Density screening (with and without IFB),
which should be insignificant.
"""
mol = psi4.geometry("""
0 1
O -1.551007 -0.114520 0.000000
H -1.934259 0.762503 0.000000
H -0.599677 0.040712 0.000000
O 1.350625 0.111469 0.000000
H 1.680398 -0.373741 -0.758561
H 1.680398 -0.373741 0.758561
symmetry c1
no_reorient
no_com
""")
psi4.set_options({
'scf_type': 'direct',
'd_convergence': 1e-6,
'df_scf_guess': False,
'screening': 'schwarz',
'ints_tolerance': 1.0e-12
})
e_schwarz = psi4.energy('hf/DZ')
psi4.core.clean()
psi4.set_options({
'scf_type': 'direct',
'd_convergence': 1e-6,
'df_scf_guess': False,
'screening': 'density',
'incfock': False,
'ints_tolerance': 1.0e-12
})
e_density = psi4.energy('hf/DZ')
psi4.core.clean()
psi4.set_options({
'scf_type': 'direct',
'd_convergence': 1e-6,
'df_scf_guess': False,
'screening': 'density',
'incfock': True,
'ints_tolerance': 1.0e-12
})
e_incfock = psi4.energy('hf/DZ')
assert compare_values(e_schwarz, e_density, 10,
'Schwarz vs Density Screening, Cutoff 1.0e-12')
assert compare_values(e_schwarz, e_incfock, 10,
'Schwarz vs Density Screening, Cutoff 1.0e-12')
def test_RU_TDA_C1():
h2o = psi4.geometry("""0 1
O 0.000000 0.000000 0.135446
H -0.000000 0.866812 -0.541782
H -0.000000 -0.866812 -0.541782
symmetry c1
no_reorient
no_com
""")
psi4.set_options({"scf_type": "pk", 'save_jk': True})
e, wfn = psi4.energy("hf/sto-3g", molecule=h2o, return_wfn=True)
A_ref, _ = build_UHF_AB_C1(wfn)
ni, na, _, _ = A_ref['IAJB'].shape
nia = ni * na
A_sing_ref = A_ref['IAJB'] + A_ref['IAjb']
A_sing_ref = A_sing_ref.reshape(nia, nia)
A_trip_ref = A_ref['IAJB'] - A_ref['IAjb']
A_trip_ref = A_trip_ref.reshape(nia, nia)
sing_vals, _ = np.linalg.eigh(A_sing_ref)
trip_vals, _ = np.linalg.eigh(A_trip_ref)
trip_eng = TDRSCFEngine(wfn, ptype='tda', triplet=True)
sing_eng = TDRSCFEngine(wfn, ptype='tda', triplet=False)
ID = [
psi4.core.Matrix.from_array(v.reshape((ni, na)))
for v in tuple(np.eye(nia).T)
]
psi4.core.print_out("\nA sing:\n" + str(A_sing_ref) + "\n\n")
psi4.core.print_out("\nA trip:\n" + str(A_trip_ref) + "\n\n")
A_trip_test = np.column_stack(
[x.to_array().flatten() for x in trip_eng.compute_products(ID)[0]])
assert compare_arrays(A_trip_ref, A_trip_test, 8, "Triplet Ax C1 products")
A_sing_test = np.column_stack(
[x.to_array().flatten() for x in sing_eng.compute_products(ID)[0]])
assert compare_arrays(A_sing_ref, A_sing_test, 8, "Singlet Ax C1 products")
sing_vals_2, _ = np.linalg.eigh(A_sing_test)
trip_vals_2, _ = np.linalg.eigh(A_trip_test)
psi4.core.print_out("\n\n SINGLET EIGENVALUES\n")
for x, y in zip(sing_vals, sing_vals_2):
psi4.core.print_out("{:10.6f} {:10.6f}\n".format(x, y))
# assert compare_values(x, y, 4, "Singlet ROOT")
psi4.core.print_out("\n\n Triplet EIGENVALUES\n")
for x, y in zip(trip_vals, trip_vals_2):
psi4.core.print_out("{:10.6f} {:10.6f}\n".format(x, y))
# assert compare_values(x, y, 4, "Triplet Root")
for x, y in zip(sing_vals, sing_vals_2):
assert compare_values(x, y, 4, "Singlet ROOT")
for x, y in zip(trip_vals, trip_vals_2):
assert compare_values(x, y, 4, "Triplet Root")
def test_schwarz_vs_csam_energy():
"""Checks difference in Hartree-Fock energy between no screening and CSAM screening, which should be
insignificant. """
psi4.geometry("""
Ne 0.0 0.0 0.0
Ne 4.0 0.0 0.0
Ne 8.0 0.0 0.0
""")
psi4.set_options({
'scf_type': 'direct',
'd_convergence': 1e-12,
'screening': 'schwarz',
'ints_tolerance': 1.0e-12
})
e_schwarz = psi4.energy('hf/DZ')
psi4.core.clean()
psi4.set_options({
'scf_type': 'direct',
'd_convergence': 1e-12,
'screening': 'csam',
'ints_tolerance': 1.0e-12
})
e_csam = psi4.energy('hf/DZ')
assert compare_values(e_schwarz, e_csam, 11,
'Schwarz vs CSAM Screening, Cutoff 1.0e-12')
def test_dipole(inp):
h2o = psi4.geometry("""
O
H 1 1.0
H 1 1.0 2 101.5
""")
psi4.set_options({
'perturb_h': True,
'perturb_with': 'dipole',
'basis': 'cc-pvdz'
})
psi4.set_options(inp['options'])
energies = dict()
for l in [1, -1, 2, -2]:
psi4.set_options({'perturb_dipole': [0, 0, l * perturbation_strength]})
energies[l] = psi4.energy(inp['name'])
findif_dipole = [
0, 0,
(8 * energies[1] - 8 * energies[-1] - energies[2] + energies[-2]) /
(12 * perturbation_strength)
]
psi4.set_options({'perturb_h': False})
wfn = psi4.properties(inp['name'], properties=['dipole'],
return_wfn=True)[1]
analytic_dipole = wfn.variable(inp['varname'] + " DIPOLE")
assert compare_values(findif_dipole, analytic_dipole, 5,
"findif vs. analytic dipole")
def test_RU_TDA_C1():
h2o = psi4.geometry("""0 1
O 0.000000 0.000000 0.135446
H -0.000000 0.866812 -0.541782
H -0.000000 -0.866812 -0.541782
symmetry c1
no_reorient
no_com
""")
psi4.set_options({"scf_type": "pk", 'save_jk': True})
e, wfn = psi4.energy("hf/sto-3g", molecule=h2o, return_wfn=True)
A_ref, _ = build_UHF_AB_C1(wfn)
ni, na, _, _ = A_ref['IAJB'].shape
nia = ni * na
A_sing_ref = A_ref['IAJB'] + A_ref['IAjb']
A_sing_ref = A_sing_ref.reshape(nia, nia)
A_trip_ref = A_ref['IAJB'] - A_ref['IAjb']
A_trip_ref = A_trip_ref.reshape(nia, nia)
sing_vals, _ = np.linalg.eigh(A_sing_ref)
trip_vals, _ = np.linalg.eigh(A_trip_ref)
trip_eng = TDRSCFEngine(wfn, ptype='tda', triplet=True)
sing_eng = TDRSCFEngine(wfn, ptype='tda', triplet=False)
ID = [psi4.core.Matrix.from_array(v.reshape((ni, na))) for v in tuple(np.eye(nia).T)]
psi4.core.print_out("\nA sing:\n" + str(A_sing_ref) + "\n\n")
psi4.core.print_out("\nA trip:\n" + str(A_trip_ref) + "\n\n")
A_trip_test = np.column_stack([x.to_array().flatten() for x in trip_eng.compute_products(ID)[0]])
assert compare_arrays(A_trip_ref, A_trip_test, 8, "Triplet Ax C1 products")
A_sing_test = np.column_stack([x.to_array().flatten() for x in sing_eng.compute_products(ID)[0]])
assert compare_arrays(A_sing_ref, A_sing_test, 8, "Singlet Ax C1 products")
sing_vals_2, _ = np.linalg.eigh(A_sing_test)
trip_vals_2, _ = np.linalg.eigh(A_trip_test)
psi4.core.print_out("\n\n SINGLET EIGENVALUES\n")
for x, y in zip(sing_vals, sing_vals_2):
psi4.core.print_out("{:10.6f} {:10.6f}\n".format(x, y))
# assert compare_values(x, y, 4, "Singlet ROOT")
psi4.core.print_out("\n\n Triplet EIGENVALUES\n")
for x, y in zip(trip_vals, trip_vals_2):
psi4.core.print_out("{:10.6f} {:10.6f}\n".format(x, y))
# assert compare_values(x, y, 4, "Triplet Root")
for x, y in zip(sing_vals, sing_vals_2):
assert compare_values(x, y, 4, "Singlet ROOT")
for x, y in zip(trip_vals, trip_vals_2):
assert compare_values(x, y, 4, "Triplet Root")
def test_gradient(inp):
h2o = psi4.geometry("""
O
H 1 0.958
H 1 0.958 2 104.5
""")
psi4.set_options({'basis': 'aug-cc-pvdz', 'points': 5})
psi4.set_options(inp['options'])
analytic_gradient = psi4.gradient(inp['name'], dertype=1)
print(analytic_gradient)
findif_gradient = psi4.gradient(inp['name'], dertype=0)
reference_gradient = inp["ref"]
assert compare_values(findif_gradient, analytic_gradient, 5,
"analytic vs. findif gradient")
assert compare_values(reference_gradient, analytic_gradient.np, 5,
"analytic vs. reference gradient")
def test_dfjcosk(inp, mols):
"""Test the DFJCOSK JK object via SCF calculations"""
molecule = mols[inp["molecule"]]
psi4.set_options({"scf_type": "cosx", "basis": "cc-pvdz"})
psi4.set_options(inp["options"])
# does the DFJCOSK SCF energy match a pre-computed reference?
energy_dfjcosk = psi4.energy(inp["method"],
molecule=molecule,
bsse_type=inp["bsse_type"])
assert compare_values(inp["ref"], energy_dfjcosk, atol=1e-6)
# is the DFJCOSK SCF energy reasonably close to a conventional SCF?
psi4.set_options({"scf_type": "pk"})
energy_pk = psi4.energy(inp["method"],
molecule=molecule,
bsse_type=inp["bsse_type"])
assert compare_values(energy_pk, energy_dfjcosk, atol=1e-4)
def test_weird_basis(subject, bas, ans, mols, request):
"""non-consecutive angular momentum basis set patterns"""
mol = mols[subject]
ref = "rhf" if mol.multiplicity() == 1 else "uhf"
psi4.set_options({
"reference": ref,
"guess": "core",
"scf_type": "pk",
"df_scf_guess": "false",
"basis": "anonymous1234",
})
def basisspec_psi4_yo__anonymous1234(mol, role):
mol.set_basis_all_atoms("test", role=role)
return {"test": bas}
psi4.driver.qcdb.libmintsbasisset.basishorde[
"ANONYMOUS1234"] = basisspec_psi4_yo__anonymous1234
ene = psi4.energy("scf", molecule=mol)
assert compare_values(ans, ene, 6, request.node.name)