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 test_cc_uhf_raise2():
psi4.geometry("""
0 1
O
H 1 1.0
H 1 1.0 2 104.5
""")
psi4.set_options({"reference": "uhf"})
with pytest.raises(psi4.ValidationError) as e:
psi4.properties("ccsd/sto-3g", properties=['polarizability'])
assert "Non-RHF CC response properties are not implemented." in str(e.value)
def test_pe_adc1():
"""LR-PE-ADC(1)/sto-3g formaldehyde in presence of 6 water molecules
cross-reference against PE-CIS from Psi4 itself"""
mol = psi4.geometry(__geoms['formaldehyde'])
potfile = _dump_potential('pna_6w')
psi4.set_options({
'basis': 'sto-3g',
'pe': True,
'scf_type': 'pk',
'pe__potfile': potfile,
'roots_per_irrep': [5],
'qc_module': 'adcc',
'tdscf_states': 5,
'tdscf_tda': True,
})
_, wfn_tdhf = psi4.energy('td-hf', return_wfn=True)
_, wfn_adc = psi4.properties('adc(1)',
properties=["oscillator_strength", "dipole"],
environment='linear_response',
return_wfn=True)
for i in range(5):
assert compare_values(
wfn_tdhf.variable(f'TD-HF ROOT 0 -> ROOT {i+1} EXCITATION ENERGY'),
wfn_adc.variable(f'ADC ROOT 0 -> ROOT {i+1} EXCITATION ENERGY'), 5,
f"PE-ADC(1) Excitation Energy Root {i+1}")
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_pe_adc2():
"""PE-ADC(2)/cc-pvdz formaldehyde in presence of 6 water molecules
including ptSS/ptLR corrections for excitation energies
Reference data from Q-Chem calculation"""
mol = psi4.geometry(__geoms['formaldehyde'])
potfile = _dump_potential('fa_6w')
psi4.set_options({
'basis': 'cc-pvdz',
'pe': True,
'scf_type': 'pk',
'pe__potfile': potfile,
'roots_per_irrep': [5],
'qc_module': 'adcc',
})
_, wfn = psi4.properties('adc(2)', properties=["oscillator_strength", "dipole"],
environment=True, return_wfn=True)
energies_uncorrected = [0.15963251547743104, 0.3125861355885466, 0.36222631191059046,
0.37972031238708653, 0.4118959244399415]
pe_ptlr_correction = [-2.9325959339722013e-05, -0.0002702545175242051,
-9.683446473705203e-05, -0.0001339512804427152,
-0.00270463988662346]
pe_ptss_correction = [-0.0005980584740534286, -0.00275711791912612,
-0.0008560754671915091, -0.0017443433408762471,
-0.0005800145567153289]
ref_energies = np.array(energies_uncorrected)
ref_energies += np.array(pe_ptlr_correction) + np.array(pe_ptss_correction)
for i in range(5):
en = wfn.variable(f"ADC(2) ROOT 0 -> ROOT {i+1} EXCITATION ENERGY")
assert compare_values(en, ref_energies[i], 5, f"pt-PE-ADC(2) Excitation Energy Root {i+1}")
def test_cppe_scf_alpha():
"""Tests the PE-SCF ground state energies and static dipole polarizability"""
alpha_diag = [36.14995, 35.10354, 78.45963]
ref_pe_energy = -0.03424830892844
ref_scf_energy = -482.9411084900
mol = psi4.geometry(__geoms['pna'])
potfile = _dump_potential('pna_6w')
psi4.set_options({
'basis': 'sto-3g',
'pe': True,
'e_convergence': 10,
'd_convergence': 10,
'scf_type': 'pk',
'pe__potfile': potfile,
})
scf_energy, wfn = psi4.properties("SCF",
properties=["DIPOLE_POLARIZABILITIES"],
return_wfn=True)
assert compare_values(ref_pe_energy, wfn.variable("PE ENERGY"), 6,
"PE Energy contribution")
assert compare_values(ref_scf_energy, scf_energy, 6, "Total PE-SCF Energy")
alpha_ref = [
psi4.core.variable(f'DIPOLE POLARIZABILITY {cc}')
for cc in ['XX', 'YY', 'ZZ']
]
assert compare_arrays(alpha_diag, alpha_ref, 4, 'PE DIPOLE POLARIZABILITY')
def _compute_monomers(self):
"Compute monomer wavefunctions in aggregate-centred basis set"
self.nmo_t = 0
ofm_n = 0
ofb_n = 0
for n in range(self.aggregate.nfragments()):
id_m = [n + 1]
if self.acbs is True:
id_g = list(range(1, self.aggregate.nfragments() + 1))
id_g.pop(n)
current_molecule = self.aggregate.extract_subsets(id_m, id_g)
else:
current_molecule = self.aggregate.extract_subsets(id_m)
c_ene, c_wfn = psi4.properties(
self.method,
molecule=current_molecule,
return_wfn=True,
properties=['DIPOLE', 'NO_OCCUPATIONS'],
**self.kwargs)
if self.method.lower().startswith('cc') and self.cc_relax is True:
psi4.core.set_global_option("DERTYPE", "FIRST")
psi4.core.set_global_option("WFN", self.method.upper())
psi4.core.ccdensity(c_wfn)
D = c_wfn.Da().to_array(dense=True)
N, C = self.natural_orbitals(D,
S=c_wfn.S().to_array(dense=True),
C=c_wfn.Ca_subset(
"AO", "ALL").to_array(dense=True),
orthogonalize_mo=True,
order='descending',
no_cutoff=0.0,
return_ao_orthogonal=False,
ignore_large_n=False,
renormalize=False,
n_eps=self.n_eps)
if self.verbose is True:
print("Sum of natural orbital occupations for n(%d)= %13.6f" %
(n, N.sum()))
self.data['wfn'].append(c_wfn)
self.data['ene'].append(c_ene)
self.data['odm'].append(D)
self.data['non'].append(N)
self.data['noc'].append(C)
self.data['nmo'].append(C.shape[1])
self.nmo_t += self.data['nmo'][n]
self.data['nbf'].append(c_wfn.basisset().nbf())
self.data['ofm'].append(ofm_n)
self.data['ofb'].append(ofb_n)
ofm_n += self.data['nmo'][n]
if self.acbs is False:
ofb_n += self.data['nbf'][n]
psi4.core.clean()
return
def test_H2O_density_molden(inp_h2o_density, datadir):
mol = psi4.geometry("""
0 1
O
H 1 0.951342
H 1 0.951342 2 112.505645
""")
psi4.set_options({'basis': 'dz', 'scf_type': 'pk', 'r_convergence': 12})
molden_file = f"{inp_h2o_density['name']}.molden"
ref = datadir.join(f"{inp_h2o_density['name']}.ref")
e, wfn = psi4.properties(inp_h2o_density['energy'],
return_wfn=True,
molecule=mol)
wfn.write_molden(molden_file,
do_virtual=inp_h2o_density['do_virtual'],
use_natural=inp_h2o_density['use_natural'])
assert compare_moldenfiles(ref, molden_file)
def compute_full_QM(self):
"Compute full QM interaction energy"
assert self.monomers_computed is True
self.aggregate.activate_all_fragments()
c_ene, c_wfn = psi4.properties(self.method,
molecule=self.aggregate,
return_wfn=True,
properties=["DIPOLE", "NO_OCCUPATIONS"],
**self.kwargs)
if self.method.lower().startswith('cc') and self.cc_relax is True:
psi4.core.set_global_option("DERTYPE", "FIRST")
psi4.core.set_global_option("WFN", self.method.upper())
psi4.core.ccdensity(c_wfn)
D = c_wfn.Da().to_array(dense=True)
S = c_wfn.S().to_array(dense=True)
C_hf = c_wfn.Ca_subset("AO", "ALL").to_array(dense=True)
N, C = self.natural_orbitals(D,
S=S,
C=C_hf,
orthogonalize_mo=True,
order='descending',
no_cutoff=0.0,
return_ao_orthogonal=False,
ignore_large_n=False,
renormalize=False,
n_eps=self.n_eps)
if self.verbose is True:
print("Sum of natural orbital occupations for nqm= %13.6f" %
N.sum())
self.matrix["dqm"] = D
self.matrix["nqm"] = N
self.matrix["cqm"] = C
self.matrix["sqm"] = S
self.matrix["chf"] = C_hf
e_fqm_t = c_ene
for i in range(self.aggregate.nfragments()):
e_fqm_t -= self.data["ene"][i]
self.vars["e_fqm_t"] = e_fqm_t
self.energy_full_QM_computed = True
return
def test_psi4_scfproperty():
"""scf-property"""
#! UFH and B3LYP cc-pVQZ properties for the CH2 molecule.
ref_hf_di_au = np.array([0.0, 0.0, 0.22531665104559076])
ref_hf_quad_au = np.array([[-5.69804565317, 0.0, 0.0],
[0.0, -4.53353128969, 0.0],
[0.0, 0.0, -5.25978856037]])
ref_b3lyp_di_au = np.array([0.0, 0.0, 0.252480541747])
ref_b3lyp_quad_au = np.array([[-5.66266837697, 0.0, 0.0],
[0.0, -4.46523692003, 0.0],
[0.0, 0.0, -5.22054902407]])
with open('grid.dat', 'w') as handle:
handle.write("""\
0.0 0.0 0.0
1.1 1.3 1.4
""")
ch2 = psi4.geometry("""
0 3
c
h 1 b1
h 1 b1 2 a1
b1 = 1.0
a1 = 125.0
""")
# Get a reasonable guess, to save some iterations
psi4.set_options({
"scf_type": "pk",
"basis": "6-31G**",
"e_convergence": 8,
"docc": [2, 0, 0, 1],
"socc": [1, 0, 1, 0],
"reference": "uhf"
})
ch2.update_geometry()
assert psi4.compare_values(6.6484189450, ch2.nuclear_repulsion_energy(), 9,
"Nuclear repulsion energy")
props = [
'DIPOLE', 'QUADRUPOLE', 'MULLIKEN_CHARGES', 'LOWDIN_CHARGES',
'WIBERG_LOWDIN_INDICES', 'MAYER_INDICES', 'MAYER_INDICES',
'MO_EXTENTS', 'GRID_FIELD', 'GRID_ESP', 'ESP_AT_NUCLEI',
'MULTIPOLE(5)', 'NO_OCCUPATIONS'
]
psi4.properties('scf', properties=props)
assert psi4.compare_values(-38.91591819679808,
psi4.variable("CURRENT ENERGY"), 6,
"SCF energy")
assert psi4.compare_values(ref_hf_di_au, psi4.variable('SCF DIPOLE'), 4,
"SCF DIPOLE")
assert psi4.compare_values(ref_hf_quad_au, psi4.variable('SCF QUADRUPOLE'),
4, "SCF QUADRUPOLE")
psi4.properties('B3LYP', properties=props)
assert psi4.compare_values(psi4.variable('CURRENT ENERGY'),
-39.14134740550916, 6, "B3LYP energy")
assert psi4.compare_values(ref_b3lyp_di_au, psi4.variable('B3LYP DIPOLE'),
4, "B3LYP DIPOLE")
assert psi4.compare_values(ref_b3lyp_quad_au,
psi4.variable('B3LYP QUADRUPOLE'), 4,
"B3LYP QUADRUPOLE")
def run(input_json):
# detect custom psi4, if we can
psiapi_path = os.environ.get('PSIAPI_PATH')
if psiapi_path:
sys.path.insert(1, psiapi_path)
import psi4
mol_json = input_json.pop('molecule')
mc_json = input_json.pop('modelchem')
output_json = {}
output_json['raw_output'] = {}
output_json['success'] = False
output_json['output'] = {}
# set some psi4 global stuff
# Scratch files
scr_path = os.environ.get("WORK")
psi4_io = psi4.core.IOManager.shared_object()
psi4_io.set_default_path(scr_path)
# raw output file
outfile_path = Path('output.dat')
psi4.core.set_output_file(str(outfile_path), False)
# node (or configured) memory and cores (after setting output file so the changes are registered there?)
psi4.set_memory(str(cpu_info.memory()) + " MB")
psi4.set_num_threads(cpu_info.ncore())
# set the basis
basis = mc_json.get('basis')
psi4.core.set_global_option('basis', basis)
# set any other options
for k, v in mc_json.get('program_options', {}).items():
psi4.core.set_global_option(k, v)
try:
# create the molecule
psi_mol = psi4.geometry(vicMol(mol_json, dtype='json').to_string())
# extract name
method = mc_json.get('method')
driver = mc_json.get('driver')
if driver == 'gradient':
ret, wfn = psi4.gradient(method, return_wfn=True, molecule =psi_mol)
elif driver == 'hessian':
ret, wfn = psi4.hessian(method, return_wfn = True, molecule = psi_mol)
elif driver == 'rotation':
ret, wfn = psi4.properties(method, return_wfn = True, molecule = psi_mol, properties=['rotation'])
else:
raise RuntimeError("invalid driver {}: Validation should have caught this".format(driver))
grad = wfn.gradient()
hess = wfn.hessian()
rotations = extract_rotations(psi4.core.get_variables())
if hess:
output_json['output']['hessian'] = util.pack_json_field(hess.to_array())
if grad:
output_json['output']['gradient'] = util.pack_json_field(grad.to_array())
if rotations:
output_json['output']['rotations'] = rotations
output_json['output']['all_variables'] = psi4.core.get_variables()
output_json['success'] = True
output_json['raw_output']['outfile'] = outfile_path.read_text()
return output_json
except Exception as e:
output_json['success'] = False
output_json['raw_output']['error'] = "\n".join(traceback.format_exception(*sys.exc_info()))
return output_json
psi4.set_memory('2 GB')
psi4.core.set_output_file('optrot.dat', False)
np.set_printoptions(precision=12,
threshold=np.inf,
linewidth=200,
suppress=True)
# Set Psi4 options
geom = ccsd_lpno.mollib.mollib["{}".format(args.m)]
mol = psi4.geometry(geom)
psi4.set_options({
'basis': 'aug-cc-pvdz',
'scf_type': 'pk',
'freeze_core': 'false',
'e_convergence': 1e-12,
'd_convergence': 1e-12,
'save_jk': 'true'
})
psi4.set_options({'omega': [589, 'nm'], 'gauge': 'both'})
psi4.properties('ccsd', properties=['rotation', 'polarizability'])
print("Correlation energy: {}".format(
psi4.core.variable("CCSD CORRELATION ENERGY")))
print("Optical rotation (LG): {}".format(
psi4.core.variable("CCSD SPECIFIC ROTATION (LEN) @ 589NM")))
print("Optical rotation (MVG): {}".format(
psi4.core.variable("CCSD SPECIFIC ROTATION (MVG) @ 589NM")))
print("Polarizability: {}".format(
psi4.core.variable("CCSD DIPOLE POLARIZABILITY @ 589NM")))
def test_psi4_scfproperty():
"""scf-property"""
#! UFH and B3LYP cc-pVQZ properties for the CH2 molecule.
with open('grid.dat', 'w') as handle:
handle.write("""\
0.0 0.0 0.0
1.1 1.3 1.4
""")
ch2 = psi4.geometry("""
0 3
c
h 1 b1
h 1 b1 2 a1
b1 = 1.0
a1 = 125.0
""")
# Get a reasonable guess, to save some iterations
psi4.set_options({
"scf_type": "pk",
"basis": "6-31G**",
"e_convergence": 8,
"docc": [2, 0, 0, 1],
"socc": [1, 0, 1, 0],
"reference": "uhf"})
ch2.update_geometry()
assert psi4.compare_values(6.648418918908746, ch2.nuclear_repulsion_energy(), 9, "Nuclear repulsion energy")
props = ['DIPOLE', 'QUADRUPOLE', 'MULLIKEN_CHARGES', 'LOWDIN_CHARGES',
'WIBERG_LOWDIN_INDICES', 'MAYER_INDICES', 'MAYER_INDICES',
'MO_EXTENTS', 'GRID_FIELD', 'GRID_ESP', 'ESP_AT_NUCLEI',
'MULTIPOLE(5)', 'NO_OCCUPATIONS']
psi4.properties('scf', properties=props)
assert psi4.compare_values(psi4.get_variable("CURRENT ENERGY"), -38.91591819679808, 6, "SCF energy")
assert psi4.compare_values(psi4.get_variable('SCF DIPOLE X'), 0.000000000000, 4, "SCF DIPOLE X")
assert psi4.compare_values(psi4.get_variable('SCF DIPOLE Y'), 0.000000000000, 4, "SCF DIPOLE Y")
assert psi4.compare_values(psi4.get_variable('SCF DIPOLE Z'), 0.572697798348, 4, "SCF DIPOLE Z")
assert psi4.compare_values(psi4.get_variable('SCF QUADRUPOLE XX'), -7.664066833060, 4, "SCF QUADRUPOLE XX")
assert psi4.compare_values(psi4.get_variable('SCF QUADRUPOLE YY'), -6.097755074075, 4, "SCF QUADRUPOLE YY")
assert psi4.compare_values(psi4.get_variable('SCF QUADRUPOLE ZZ'), -7.074596012050, 4, "SCF QUADRUPOLE ZZ")
assert psi4.compare_values(psi4.get_variable('SCF QUADRUPOLE XY'), 0.000000000000, 4, "SCF QUADRUPOLE XY")
assert psi4.compare_values(psi4.get_variable('SCF QUADRUPOLE XZ'), 0.000000000000, 4, "SCF QUADRUPOLE XZ")
assert psi4.compare_values(psi4.get_variable('SCF QUADRUPOLE YZ'), 0.000000000000, 4, "SCF QUADRUPOLE YZ")
psi4.properties('B3LYP', properties=props)
assert psi4.compare_values(psi4.get_variable('CURRENT ENERGY'), -39.14134740550916, 6, "B3LYP energy")
assert psi4.compare_values(psi4.get_variable('B3LYP DIPOLE X'), 0.000000000000, 4, "B3LYP DIPOLE X")
assert psi4.compare_values(psi4.get_variable('B3LYP DIPOLE Y'), -0.000000000000, 4, "B3LYP DIPOLE Y")
assert psi4.compare_values(psi4.get_variable('B3LYP DIPOLE Z'), 0.641741521158, 4, "B3LYP DIPOLE Z")
assert psi4.compare_values(psi4.get_variable('B3LYP QUADRUPOLE XX'), -7.616483183211, 4, "B3LYP QUADRUPOLE XX")
assert psi4.compare_values(psi4.get_variable('B3LYP QUADRUPOLE YY'), -6.005896804551, 4, "B3LYP QUADRUPOLE YY")
assert psi4.compare_values(psi4.get_variable('B3LYP QUADRUPOLE ZZ'), -7.021817489904, 4, "B3LYP QUADRUPOLE ZZ")
assert psi4.compare_values(psi4.get_variable('B3LYP QUADRUPOLE XY'), 0.000000000000, 4, "B3LYP QUADRUPOLE XY")
assert psi4.compare_values(psi4.get_variable('B3LYP QUADRUPOLE XZ'), 0.000000000000, 4, "B3LYP QUADRUPOLE XZ")
assert psi4.compare_values(psi4.get_variable('B3LYP QUADRUPOLE YZ'), -0.000000000000, 4, "B3LYP QUADRUPOLE YZ")
"""
)
nroots = 3
psi4.set_options(
{
"basis": "6-31G*",
"freeze_core": "true",
"roots_per_irrep": [nroots],
"pe": "true",
"puream": "true",
"ints_tolerance": 2.5e-11,
}
)
psi4.set_module_options("pe", {"potfile": "nilered_in_water.pot", "maxiter": 200})
psi4.set_module_options("ccenergy", {"cachelevel": 0})
psi4.set_module_options("cclambda", {"r_convergence": 1e-3, "cachelevel": 0})
psi4.set_module_options(
"cceom", {"cachelevel": 0, "r_convergence": 1e-3, "e_convergence": 1e-5}
)
cce, ccwfn = psi4.properties(
"eom-cc2", properties=["dipole"], return_wfn=True, molecule=mol
)
ptss = compute_ptss_corrections(ccwfn, nroots)
(cart[0], cart[1], cart[2]))
for a in range(0, 3):
print(" %s %20.10lf %20.10lf %20.10lf\n" %
(cart[a], polar_AB[3 * a + 0], polar_AB[3 * a + 1],
polar_AB[3 * a + 2]))
# Isotropic polarizability
trace = polar_AB[0] + polar_AB[4] + polar_AB[8]
Isotropic_polar = trace / 3.0
print(
" Isotropic CCSD Dipole Polarizability @ %d nm (Length Gauge): %20.10lf a.u."
% (omega_nm, Isotropic_polar))
# Comaprison with PSI4 (if you have near to latest version of psi4)
psi4.set_options({'d_convergence': 1e-10})
psi4.set_options({'e_convergence': 1e-10})
psi4.set_options({'r_convergence': 1e-10})
psi4.set_options({'omega': [589, 'nm']})
psi4.properties('ccsd', properties=['polarizability'])
psi4.compare_values(
Isotropic_polar, psi4.variable("CCSD DIPOLE POLARIZABILITY @ 589NM"), 6,
"CCSD Isotropic Dipole Polarizability @ 589 nm (Length Gauge)") #TEST
#psi4.compare_values(
# Isotropic_polar, 8.5698293248, 6,
# "CCSD Isotropic Dipole Polarizability @ 589 nm (Length Gauge)") # TEST
# Optical rotation
def test_psi4_scfproperty():
"""scf-property"""
#! UFH and B3LYP cc-pVQZ properties for the CH2 molecule.
with open('grid.dat', 'w') as handle:
handle.write("""\
0.0 0.0 0.0
1.1 1.3 1.4
""")
ch2 = psi4.geometry("""
0 3
c
h 1 b1
h 1 b1 2 a1
b1 = 1.0
a1 = 125.0
""")
# Get a reasonable guess, to save some iterations
psi4.set_options({
"scf_type": "pk",
"basis": "6-31G**",
"e_convergence": 8,
"docc": [2, 0, 0, 1],
"socc": [1, 0, 1, 0],
"reference": "uhf"
})
ch2.update_geometry()
assert psi4.compare_values(6.6484189450, ch2.nuclear_repulsion_energy(), 9,
"Nuclear repulsion energy")
props = [
'DIPOLE', 'QUADRUPOLE', 'MULLIKEN_CHARGES', 'LOWDIN_CHARGES',
'WIBERG_LOWDIN_INDICES', 'MAYER_INDICES', 'MAYER_INDICES',
'MO_EXTENTS', 'GRID_FIELD', 'GRID_ESP', 'ESP_AT_NUCLEI',
'MULTIPOLE(5)', 'NO_OCCUPATIONS'
]
psi4.properties('scf', properties=props)
assert psi4.compare_values(psi4.get_variable("CURRENT ENERGY"),
-38.91591819679808, 6, "SCF energy")
assert psi4.compare_values(psi4.get_variable('SCF DIPOLE X'),
0.000000000000, 4, "SCF DIPOLE X")
assert psi4.compare_values(psi4.get_variable('SCF DIPOLE Y'),
0.000000000000, 4, "SCF DIPOLE Y")
assert psi4.compare_values(psi4.get_variable('SCF DIPOLE Z'),
0.572697798348, 4, "SCF DIPOLE Z")
assert psi4.compare_values(psi4.get_variable('SCF QUADRUPOLE XX'),
-7.664066833060, 4, "SCF QUADRUPOLE XX")
assert psi4.compare_values(psi4.get_variable('SCF QUADRUPOLE YY'),
-6.097755074075, 4, "SCF QUADRUPOLE YY")
assert psi4.compare_values(psi4.get_variable('SCF QUADRUPOLE ZZ'),
-7.074596012050, 4, "SCF QUADRUPOLE ZZ")
assert psi4.compare_values(psi4.get_variable('SCF QUADRUPOLE XY'),
0.000000000000, 4, "SCF QUADRUPOLE XY")
assert psi4.compare_values(psi4.get_variable('SCF QUADRUPOLE XZ'),
0.000000000000, 4, "SCF QUADRUPOLE XZ")
assert psi4.compare_values(psi4.get_variable('SCF QUADRUPOLE YZ'),
0.000000000000, 4, "SCF QUADRUPOLE YZ")
psi4.properties('B3LYP', properties=props)
assert psi4.compare_values(psi4.get_variable('CURRENT ENERGY'),
-39.14134740550916, 6, "B3LYP energy")
assert psi4.compare_values(psi4.get_variable('B3LYP DIPOLE X'),
0.000000000000, 4, "B3LYP DIPOLE X")
assert psi4.compare_values(psi4.get_variable('B3LYP DIPOLE Y'),
-0.000000000000, 4, "B3LYP DIPOLE Y")
assert psi4.compare_values(psi4.get_variable('B3LYP DIPOLE Z'),
0.641741521158, 4, "B3LYP DIPOLE Z")
assert psi4.compare_values(psi4.get_variable('B3LYP QUADRUPOLE XX'),
-7.616483183211, 4, "B3LYP QUADRUPOLE XX")
assert psi4.compare_values(psi4.get_variable('B3LYP QUADRUPOLE YY'),
-6.005896804551, 4, "B3LYP QUADRUPOLE YY")
assert psi4.compare_values(psi4.get_variable('B3LYP QUADRUPOLE ZZ'),
-7.021817489904, 4, "B3LYP QUADRUPOLE ZZ")
assert psi4.compare_values(psi4.get_variable('B3LYP QUADRUPOLE XY'),
0.000000000000, 4, "B3LYP QUADRUPOLE XY")
assert psi4.compare_values(psi4.get_variable('B3LYP QUADRUPOLE XZ'),
0.000000000000, 4, "B3LYP QUADRUPOLE XZ")
assert psi4.compare_values(psi4.get_variable('B3LYP QUADRUPOLE YZ'),
-0.000000000000, 4, "B3LYP QUADRUPOLE YZ")
H 1 1.1 2 104
symmetry c1
""")
opt_dict = {
"basis": "sto-3g",
"reference": "RHF",
"print_MOs": "True",
"mp2_type": "conv",
"scf_type": "pk",
"roots_per_irrep": [40],
"e_convergence": 1e-14,
"r_convergence": 1e-14
}
psi4.set_options(opt_dict)
psi4.properties('ccsd', properties=['dipole', 'analyze'])
#psi4.properties('cc2', properties=['dipole','analyze'])
#Start parameters
#w0 frequency of the oscillation
#A = 0.005#the amplitude of the electric field
#t0 = 0.0000 #the start time
#dt = 0.0001 #time step
#precs = 15 #precision of the t1, t2, l1, l2 amplitudes
mol = CC_Calculator(psi4, w0=0.968635, A=0.005, t0=0.0, dt=0.0001, precs=15)
#Time-dependent CC2 calculation
#mol.TDCC(timeout, 'CC2')
#Time-dependent CCSD calculation
mol.TDCC(timeout, 'CCSD')
""")
mol.fix_com(True)
mol.fix_orientation(True)
psi4.core.set_num_threads(NUMTHREADS)
psi4.set_options({'basis': 'cc-pvdz'})
psi4.set_options({'maxiter': 500})
psi4.set_options({'cachelevel': CCCACHELEVEL})
psi4.set_options({'freeze_core': 'true'})
psi4.set_options({'reference': 'rhf'})
# --- HF calculation --- #
E, wf = psi4.energy('scf', molecule=mol, return_wfn=True)
# save the some matrixes
numpy.save("D-HF", wf.Da().to_array(False, True))
numpy.save("F-HF", wf.Fa().to_array(False, True))
numpy.save("C-HF", wf.Ca().to_array(False, True))
numpy.save("H-HF", wf.H().to_array(False, True))
numpy.save("e-HF", wf.epsilon_a().to_array(False, True))
props, ccwf = psi4.properties('CCSD',
molecule=mol,
properties=['MULLIKEN_CHARGES'],
return_wfn=True,
ref_wfn=wf)
# save the some matrixes
numpy.save("D-CCSD", ccwf.Da().to_array(False, True))
def test_cc_polaroptrot():
# cc29 + polarizabilities + tensors
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
noreorient
""")
mw = sum([mol.mass(i) for i in range(0, 4)])
c = psi4.constants.c
h = psi4.constants.h
h2j = psi4.constants.hartree2J
Na = psi4.constants.na
me = psi4.constants.me
hbar = psi4.constants.hbar
prefactor = -72E6 * hbar**2 * Na / c**2 / me**2 / mw / 3.0
au_589 = c * h * 1E9 / h2j / 589
au_355 = c * h * 1E9 / h2j / 355
psi4.set_options({"basis": "cc-pVDZ"})
omega = [589, 355, 'nm']
psi4.set_options({
'gauge': 'both',
'omega': omega,
'freeze_core': True,
'r_convergence': 10
})
e, wfn = psi4.properties('CCSD',
properties=["polarizability", "rotation"],
return_wfn=True)
pol_589 = 8.92296 #TEST
pol_355 = 9.16134 #TEST
rotlen_589 = -76.93388 #TEST
rotvel_589 = 850.24712 #TEST
rotmvg_589 = -179.08820 #TEST
rotlen_355 = -214.73273 #TEST
rotvel_355 = 384.88786 #TEST
rotmvg_355 = -644.44746 #TEST
polr_589 = np.trace(
wfn.variable("CCSD DIPOLE POLARIZABILITY TENSOR @ 589NM").to_array()
) / 3.0 #RESULT
polr_355 = np.trace(
wfn.variable("CCSD DIPOLE POLARIZABILITY TENSOR @ 355NM").to_array()
) / 3.0 #RESULT
rotlenr_589 = np.trace(
wfn.variable("CCSD OPTICAL ROTATION TENSOR (LEN) @ 589NM").to_array()
) * prefactor * au_589 #RESULT
rotvelr_589 = np.trace(
wfn.variable("CCSD OPTICAL ROTATION TENSOR (VEL) @ 589NM").to_array()
) * prefactor #RESULT
rotmvgr_589 = np.trace(
wfn.variable("CCSD OPTICAL ROTATION TENSOR (MVG) @ 589NM").to_array()
) * prefactor #RESULT
rotlenr_355 = np.trace(
wfn.variable("CCSD OPTICAL ROTATION TENSOR (LEN) @ 355NM").to_array()
) * prefactor * au_355 #RESULT
rotvelr_355 = np.trace(
wfn.variable("CCSD OPTICAL ROTATION TENSOR (VEL) @ 355NM").to_array()
) * prefactor #RESULT
rotmvgr_355 = np.trace(
wfn.variable("CCSD OPTICAL ROTATION TENSOR (MVG) @ 355NM").to_array()
) * prefactor #RESULT
polt_589 = np.array([[5.44184081e+00, -8.30270852e-01, 9.39878004e-14],
[-8.30270852e-01, 1.27518991e+01, -6.94720506e-14],
[9.39878004e-14, -6.94720506e-14,
8.57516214e+00]]) #TEST
polt_355 = np.array([[5.57913165e+00, -8.66951957e-01, 1.02575190e-13],
[-8.66951957e-01, 1.31256109e+01, -7.71806997e-14],
[1.02575190e-13, -7.71806997e-14,
8.77928702e+00]]) #TEST
rottvel_0 = np.array([[3.63702792e-01, -3.62754886e-01, -3.37227243e-14],
[-1.16320923e-01, 1.20784891e-02, 1.76483272e-14],
[1.90062651e-14, -2.33369227e-15,
-3.92022202e-01]]) #TEST
rottlen_589 = np.array([[1.41679366e-01, -7.07140738e-02, -2.26060131e-14],
[-2.72710108e-01, 1.28928522e-03, 1.01578936e-14],
[3.74236371e-14, 3.88522300e-15,
-1.27276912e-01]]) #TEST
rottvel_589 = np.array([[3.75624000e-01, -3.74245928e-01, -3.61489832e-14],
[-1.39409385e-01, 1.26867931e-02, 1.94630079e-14],
[2.33993608e-14, -1.61361648e-15,
-4.01726048e-01]]) #TEST
rottmvg_589 = np.array([[1.19212077e-02, -1.14910412e-02, -2.42625886e-15],
[-2.30884623e-02, 6.08303937e-04, 1.81468070e-15],
[4.39309571e-15, 7.20075789e-16,
-9.70384612e-03]]) #TEST
assert psi4.compare_values(pol_589, polr_589, 3,
"CCSD polarizability @ 589nm") #TEST
assert psi4.compare_values(pol_355, polr_355, 3,
"CCSD polarizability @ 355nm") #TEST
assert psi4.compare_values(rotlen_589, rotlenr_589, 3,
"CCSD rotation @ 589nm in length gauge") #TEST
assert psi4.compare_values(
rotvel_589, rotvelr_589, 3,
"CCSD rotation @ 589nm in velocity gauge") #TEST
assert psi4.compare_values(
rotmvg_589, rotmvgr_589, 3,
"CCSD rotation @ 589nm in modified velocity gauge") #TEST
assert psi4.compare_values(rotlen_355, rotlenr_355, 3,
"CCSD rotation @ 355nm in length gauge") #TEST
assert psi4.compare_values(
rotvel_355, rotvelr_355, 3,
"CCSD rotation @ 355nm in velocity gauge") #TEST
assert psi4.compare_values(
rotmvg_355, rotmvgr_355, 3,
"CCSD rotation @ 355nm in modified velocity gauge") #TEST
assert psi4.compare_values(
polt_589, wfn.variable("CCSD DIPOLE POLARIZABILITY TENSOR @ 589NM"), 3,
"CCSD polarizability tensor @ 589nm") #TEST
assert psi4.compare_values(
polt_355, wfn.variable("CCSD DIPOLE POLARIZABILITY TENSOR @ 355NM"), 3,
"CCSD polarizability tensor @ 355nm") #TEST
assert psi4.compare_arrays(
rottvel_0, wfn.variable("CCSD OPTICAL ROTATION TENSOR (VEL) @ 0NM"), 3,
"CCSD optrot tensor @ 0NM in velocity guage") #TEST
assert psi4.compare_arrays(
rottlen_589,
wfn.variable("CCSD OPTICAL ROTATION TENSOR (LEN) @ 589NM"), 3,
"CCSD optrot tensor @ 589NM in length guage") #TEST
assert psi4.compare_arrays(
rottvel_589,
wfn.variable("CCSD OPTICAL ROTATION TENSOR (VEL) @ 589NM"), 3,
"CCSD optrot tensor @ 589NM in velocity guage") #TEST
assert psi4.compare_arrays(
rottmvg_589,
wfn.variable("CCSD OPTICAL ROTATION TENSOR (MVG) @ 589NM"), 3,
"CCSD optrot tensor @ 589NM in modified velocity guage") #TEST
def test_cc_roa():
# three tensors for ROA (polar, optrot, and dip-quad)
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
noreorient
""")
psi4.set_options({"basis": "cc-pVDZ"})
omega = [589, 'nm']
psi4.set_options({
'gauge': 'both',
'omega': omega,
'freeze_core': True,
'r_convergence': 10
})
e, wfn = psi4.properties('CCSD',
properties=["roa_tensor"],
return_wfn=True)
polt_589 = np.array([[5.44184081e+00, -8.30270852e-01, 9.39878004e-14],
[-8.30270852e-01, 1.27518991e+01, -6.94720506e-14],
[9.39878004e-14, -6.94720506e-14, 8.57516214e+00]])
rottvel_0 = np.array([[3.63702792e-01, -3.62754886e-01, -3.37227243e-14],
[-1.16320923e-01, 1.20784891e-02, 1.76483272e-14],
[1.90062651e-14, -2.33369227e-15, -3.92022202e-01]])
rottlen_589 = np.array([[1.41679366e-01, -7.07140738e-02, -2.26060131e-14],
[-2.72710108e-01, 1.28928522e-03, 1.01578936e-14],
[3.74236371e-14, 3.88522300e-15, -1.27276912e-01]])
rottvel_589 = np.array([[3.75624000e-01, -3.74245928e-01, -3.61489832e-14],
[-1.39409385e-01, 1.26867931e-02, 1.94630079e-14],
[2.33993608e-14, -1.61361648e-15,
-4.01726048e-01]])
rottmvg_589 = np.array([[1.19212077e-02, -1.14910412e-02, -2.42625886e-15],
[-2.30884623e-02, 6.08303937e-04, 1.81468070e-15],
[4.39309571e-15, 7.20075789e-16, -9.70384612e-03]])
quad0 = np.array([[[-2.52229282e-14, -4.33846468e-13, 3.90176525e+00],
[-4.33846468e-13, -6.81906994e-15, -5.83659009e+00],
[3.90176525e+00, -5.83659009e+00, 3.18177152e-14]],
[[1.20834634e-13, 6.99638702e-14, -2.37995874e+00],
[6.99638702e-14, -1.17603861e-13, 6.85651590e+00],
[-2.37995874e+00, 6.85651590e+00, -3.99609068e-15]],
[[-4.55024365e+00, -5.30335671e+00, 1.65990108e-13],
[-5.30335671e+00, -1.35415335e+00, -8.75522529e-13],
[1.65990108e-13, -8.75522529e-13, 5.90439700e+00]]])
assert psi4.compare_values(
polt_589, wfn.variable("CCSD DIPOLE POLARIZABILITY TENSOR @ 589NM"), 3,
"CCSD polarizability tensor @ 589nm") #TEST
assert psi4.compare_arrays(
rottvel_0, wfn.variable("CCSD OPTICAL ROTATION TENSOR (VEL) @ 0NM"), 3,
"CCSD optrot tensor @ 0NM in velocity guage") #TEST
assert psi4.compare_arrays(
rottlen_589,
wfn.variable("CCSD OPTICAL ROTATION TENSOR (LEN) @ 589NM"), 3,
"CCSD optrot tensor @ 589NM in length guage") #TEST
assert psi4.compare_arrays(
rottvel_589,
wfn.variable("CCSD OPTICAL ROTATION TENSOR (VEL) @ 589NM"), 3,
"CCSD optrot tensor @ 589NM in velocity guage") #TEST
assert psi4.compare_arrays(
rottmvg_589,
wfn.variable("CCSD OPTICAL ROTATION TENSOR (MVG) @ 589NM"), 3,
"CCSD optrot tensor @ 589NM in modified velocity guage") #TEST
assert psi4.compare_values(
quad0, wfn.variable("CCSD QUADRUPOLE POLARIZABILITY TENSOR @ 589NM"),
3, "CCSD quadrupole tensor @ 589nm") #TEST
# Run this with:
# python input.py
# Make sure helper files are in the same directory
# Everything should work as intended if downloaded from github.com/yramis/rtcc
# If not, feel free to write me a strongly worded email for not keepting this repo up to date.
import psi4
from helper_tdcc import rtcc
from opt_einsum import contract
import numpy as np
mol = psi4.geometry("""
Li
H 1 1
symmetry c1
""")
psi4.set_options({'basis': 'sto-3g'})
psi4.set_options({'reference': 'rhf'})
rtcc()
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})
e_ccsd = psi4.properties('ccsd', 'dipole')
def test_adcc_reference_data(case):
conf = case["config"]
psi4.core.clean()
psi4.set_options({
'reference': conf['reference'],
'basis': conf['basis'],
'guess': 'core',
'scf_type': 'pk',
'roots_per_irrep': [conf['n_states']],
'kind': conf['kind'],
'num_core_orbitals': conf['core_orbitals'],
'freeze_core': conf['frozen_core'],
'num_frozen_uocc': conf['frozen_virtual'],
'e_convergence': 1e-10,
'd_convergence': 1e-8,
'gauge': conf['gauge'],
'adc__r_convergence': 1e-8,
})
mol = psi4.core.Molecule.from_string(conf['molstring'])
props = [
'TRANSITION_DIPOLE', 'DIPOLE', 'OSCILLATOR_STRENGTH',
'ROTATIONAL_STRENGTH'
]
en_adc, wfn = psi4.properties(conf['method'],
properties=props,
return_wfn=True,
molecule=mol)
np.testing.assert_allclose(en_adc, case['energy_gs'], atol=1e-7)
np.testing.assert_allclose(wfn.variable("CURRENT ENERGY"),
case['energy_gs'],
atol=1e-7)
method = conf['method'].upper()
for i in range(conf['n_states']):
root_index = i + 1
prop_access_patterns = {
'excitation_energy': ([
f"{method} ROOT 0 -> ROOT {root_index} EXCITATION ENERGY",
f"{method} ROOT 0 (IN A) -> ROOT {root_index} (IN A) EXCITATION ENERGY",
f"{method} ROOT 0 (A) -> ROOT {root_index} (A) EXCITATION ENERGY",
f"{method} ROOT 0 -> ROOT {root_index} EXCITATION ENERGY - A TRANSITION",
f"ADC ROOT 0 -> ROOT {root_index} EXCITATION ENERGY",
f"ADC ROOT 0 (IN A) -> ROOT {root_index} (IN A) EXCITATION ENERGY",
f"ADC ROOT 0 (A) -> ROOT {root_index} (A) EXCITATION ENERGY",
f"ADC ROOT 0 -> ROOT {root_index} EXCITATION ENERGY - A TRANSITION",
], 1e-6),
'oscillator_strength': ([
f"{method} ROOT 0 (IN A) -> ROOT {root_index} (IN A) OSCILLATOR STRENGTH (LEN)",
f"{method} ROOT 0 (A) -> ROOT {root_index} (A) OSCILLATOR STRENGTH (LEN)",
f"{method} ROOT 0 -> ROOT {root_index} OSCILLATOR STRENGTH (LEN)",
f"{method} ROOT 0 -> ROOT {root_index} OSCILLATOR STRENGTH (LEN) - A TRANSITION",
f"ADC ROOT 0 (IN A) -> ROOT {root_index} (IN A) OSCILLATOR STRENGTH (LEN)",
f"ADC ROOT 0 (A) -> ROOT {root_index} (A) OSCILLATOR STRENGTH (LEN)",
f"ADC ROOT 0 -> ROOT {root_index} OSCILLATOR STRENGTH (LEN)",
f"ADC ROOT 0 -> ROOT {root_index} OSCILLATOR STRENGTH (LEN) - A TRANSITION",
], 1e-5),
'oscillator_strength_velocity': ([
f"{method} ROOT 0 (IN A) -> ROOT {root_index} (IN A) OSCILLATOR STRENGTH (VEL)",
f"{method} ROOT 0 (A) -> ROOT {root_index} (A) OSCILLATOR STRENGTH (VEL)",
f"{method} ROOT 0 -> ROOT {root_index} OSCILLATOR STRENGTH (VEL)",
f"{method} ROOT 0 -> ROOT {root_index} OSCILLATOR STRENGTH (VEL) - A TRANSITION",
f"ADC ROOT 0 (IN A) -> ROOT {root_index} (IN A) OSCILLATOR STRENGTH (VEL)",
f"ADC ROOT 0 (A) -> ROOT {root_index} (A) OSCILLATOR STRENGTH (VEL)",
f"ADC ROOT 0 -> ROOT {root_index} OSCILLATOR STRENGTH (VEL)",
f"ADC ROOT 0 -> ROOT {root_index} OSCILLATOR STRENGTH (VEL) - A TRANSITION",
], 1e-5),
'rotatory_strength': ([
f"{method} ROOT 0 (IN A) -> ROOT {root_index} (IN A) ROTATORY STRENGTH (VEL)",
f"{method} ROOT 0 (A) -> ROOT {root_index} (A) ROTATORY STRENGTH (VEL)",
f"{method} ROOT 0 -> ROOT {root_index} ROTATORY STRENGTH (VEL)",
f"{method} ROOT 0 -> ROOT {root_index} ROTATORY STRENGTH (VEL) - A TRANSITION",
f"ADC ROOT 0 (IN A) -> ROOT {root_index} (IN A) ROTATORY STRENGTH (VEL)",
f"ADC ROOT 0 (A) -> ROOT {root_index} (A) ROTATORY STRENGTH (VEL)",
f"ADC ROOT 0 -> ROOT {root_index} ROTATORY STRENGTH (VEL)",
f"ADC ROOT 0 -> ROOT {root_index} ROTATORY STRENGTH (VEL) - A TRANSITION",
], 1e-5),
'state_dipole_moment': ([
f"{method} ROOT {root_index} (IN A) DIPOLE MOMENT",
f"{method} ROOT {root_index} (A) DIPOLE MOMENT",
f"{method} ROOT {root_index} DIPOLE MOMENT",
f"{method} ROOT {root_index} DIPOLE MOMENT - A TRANSITION",
f"ADC ROOT {root_index} (IN A) DIPOLE MOMENT",
f"ADC ROOT {root_index} (A) DIPOLE MOMENT",
f"ADC ROOT {root_index} DIPOLE MOMENT",
f"ADC ROOT {root_index} DIPOLE MOMENT - A TRANSITION",
], 5e-3),
}
for propname, (vars, atol) in prop_access_patterns.items():
# Psi lets us select only one gauge, so skip length gauge oscillator strength
# in case we have selected velocity gauge and vice versa
if propname == "oscillator_strength" and conf['gauge'] == "velocity" or \
propname == "oscillator_strength_velocity" and conf['gauge'] == "length":
continue
for v in vars:
ret = wfn.variable(v)
if isinstance(ret, psi4.core.Matrix):
ret = ret.np.flatten()
np.testing.assert_allclose(
ret,
case[propname][i],
atol=atol,
err_msg=f"Result for {v} incorrect.")
S 2 1.00
12.2874690000 0.4448700000
4.7568050000 0.2431720000
S 1 1.00
1.0042710000 1.0000000000
S 1 1.00
0.3006860000 1.0000000000
S 1 1.00
0.0900300000 1.0000000000
P 4 1.00
34.8564630000 0.0156480000
7.8431310000 0.0981970000
2.3062490000 0.3077680000
0.7231640000 0.4924700000
P 1 1.00
0.2148820000 1.0000000000
P 1 1.00
0.0638500000 1.0000000000
D 2 1.00
2.3062000000 0.2027000000
0.7232000000 0.5791000000
D 2 1.00
0.2149000000 0.7854500000
0.0639000000 0.5338700000
****
""")
ccsd_e, wfn = psi4.properties('ccsd',properties=['dipole'],return_wfn=True)
psi4.oeprop(wfn,"DIPOLE", "QUADRUPOLE", title="(OEPROP)CC")
psi4.core.print_variables()
def test_polar():
psi4.core.clean()
# Set memory
psi4.set_memory('2 GB')
psi4.core.set_output_file('test_polar_out.dat', False)
np.set_printoptions(precision=12,
threshold=np.inf,
linewidth=200,
suppress=True)
# Set Psi4 options
mol = psi4.geometry("""
0 1
O
H 1 1.1
H 1 1.1 2 104
noreorient
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
polarizability = ccsd_lpno.do_linresp(wfn,
omega_nm,
mol,
method='polar',
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']})
psi4.properties('ccsd', properties=['polarizability'])
psi4.compare_values(
polarizability,
psi4.core.variable("CCSD DIPOLE POLARIZABILITY @ 589NM"), 6,
"CCSD Isotropic Dipole Polarizability @ 589 nm (Length Gauge)") #TEST