def test_pcmsolver():
"""pcmsolver/scf"""
#! pcm
nucenergy = 12.0367196636183458
polenergy = -0.0053060443528559
totalenergy = -55.4559426361734040
NH3 = psi4.geometry("""
symmetry c1
N -0.0000000001 -0.1040380466 0.0000000000
H -0.9015844116 0.4818470201 -1.5615900098
H -0.9015844116 0.4818470201 1.5615900098
H 1.8031688251 0.4818470204 0.0000000000
units bohr
no_reorient
no_com
""")
psi4.set_options({
'basis': 'STO-3G',
'scf_type': 'pk',
'pcm': True,
'pcm_scf_type': 'total',
})
psi4.pcm_helper("""
Units = Angstrom
Medium {
SolverType = IEFPCM
Solvent = Water
}
Cavity {
RadiiSet = UFF
Type = GePol
Scaling = False
Area = 0.3
Mode = Implicit
}
""")
print('RHF-PCM, total algorithm')
energy_scf1, wfn1 = psi4.energy('scf', return_wfn=True)
assert psi4.compare_values(nucenergy, NH3.nuclear_repulsion_energy(), 10, "Nuclear repulsion energy (PCM, total algorithm)") #TEST
assert psi4.compare_values(totalenergy, energy_scf1, 10, "Total energy (PCM, total algorithm)") #TEST
assert psi4.compare_values(polenergy, wfn1.get_variable("PCM POLARIZATION ENERGY"), 6, "Polarization energy (PCM, total algorithm)") #TEST
psi4.set_options({'pcm_scf_type': 'separate'})
print('RHF-PCM, separate algorithm')
energy_scf2 = psi4.energy('scf')
assert psi4.compare_values(totalenergy, energy_scf2, 10, "Total energy (PCM, separate algorithm)")
assert psi4.compare_values(polenergy, psi4.get_variable("PCM POLARIZATION ENERGY"), 6, "Polarization energy (PCM, separate algorithm)")
# Now force use of UHF on NH3 to check sanity of the algorithm with PCM
psi4.set_options({'pcm_scf_type': 'total', 'reference': 'uhf'})
print('UHF-PCM, total algorithm')
energy_scf3 = psi4.energy('scf')
assert psi4.compare_values(totalenergy, energy_scf3, 10, "Total energy (PCM, separate algorithm)")
assert psi4.compare_values(polenergy, psi4.get_variable("PCM POLARIZATION ENERGY"), 6, "Polarization energy (PCM, separate algorithm)")
def run_psi4_tdscf(xyz,
basis,
charge=0,
multiplicity=1,
conv_tol=1e-12,
conv_tol_grad=1e-11,
max_iter=150,
pcm_options=None):
mol = psi4.geometry(f"""
{charge} {multiplicity}
{xyz}
units au
symmetry c1
""")
psi4.set_options({
'basis': basis_remap[basis],
'scf_type': "pK",
'e_convergence': conv_tol,
'd_convergence': conv_tol_grad,
'maxiter': max_iter,
'reference': "RHF",
'save_jk': True,
})
if pcm_options:
# think its better to use a dict for the pcm options, because there
# are already enough function arguments. Of course one could just
# fix the options... would be sufficient for now too.
psi4.set_options({'pcm': True, 'pcm_scf_type': "total"})
psi4.pcm_helper(f"""
Units = AU
Cavity {{
Type = Gepol
Area = {pcm_options.get("weight", 0.3)}
}}
Medium {{
Solvertype = {pcm_options.get("pcm_method", "IEFPCM")}
Solvent = {pcm_options.get("solvent", "Water")}
Nonequilibrium = {pcm_options.get("neq", True)}
}}
""")
psi4.core.be_quiet()
_, wfn = psi4.energy('scf', return_wfn=True, molecule=mol)
res = tdscf_excitations(wfn,
states=5,
triplets="NONE",
tda=True,
r_convergence=1e-7)
# remove cavity files from PSI4 PCM calculations
if pcm_options:
for cavityfile in os.listdir(os.getcwd()):
if cavityfile.startswith(("cavity.off_", "PEDRA.OUT_")):
os.remove(cavityfile)
return wfn, res
def psi4_run_pcm_hf(xyz, basis, charge=0, multiplicity=1, conv_tol=1e-12,
conv_tol_grad=1e-11, max_iter=150, pcm_options=None):
basis_map = {
"sto3g": "sto-3g",
"ccpvdz": "cc-pvdz",
}
import psi4
# needed for PE and PCM tests
psi4.core.clean_options()
mol = psi4.geometry(f"""
{charge} {multiplicity}
{xyz}
symmetry c1
units au
no_reorient
no_com
""")
psi4.core.be_quiet()
psi4.set_options({
'basis': basis_map[basis],
'scf_type': 'pk',
'e_convergence': conv_tol,
'd_convergence': conv_tol_grad,
'maxiter': max_iter,
'reference': "RHF",
"pcm": True,
"pcm_scf_type": "total",
})
psi4.pcm_helper(f"""
Units = AU
Cavity {{Type = Gepol
Area = {pcm_options.get("weight", 0.3)}}}
Medium {{Solvertype = {pcm_options.get("pcm_method", "IEFPCM")}
Nonequilibrium = {pcm_options.get("neq", True)}
Solvent = {pcm_options.get("solvent", "Water")}}}""")
if multiplicity != 1:
psi4.set_options({
'reference': "UHF",
'maxiter': max_iter + 500,
'soscf': 'true'
})
_, wfn = psi4.energy('SCF', return_wfn=True, molecule=mol)
psi4.core.clean()
return adcc.backends.import_scf_results(wfn)
def set_solvent_parameters(params, scf_obj=None):
if (params.qm_program == "psi4"):
psi4.pcm_helper("""
Units = Angstrom
Medium {
SolverType = IEFPCM
Solvent = %s
}
Cavity {
RadiiSet = UFF
Type = GePol
Scaling = False
Area = 0.3
Mode = Implicit
}
""" % params.pcm_solvent)
params.keywords['pcm'] = "true"
params.keywords['pcm_scf_type'] = "total"
if (params.qm_program == "pyscf"):
solv_obj = scf_obj.DDCOSMO()
solv_obj.with_solvent.eps = params.eps
scf_obj = solv_obj
return scf_obj
no_com
""")
psi4.set_options({
'basis': "sto-3g",
'scf_type': 'pk',
'e_convergence': 1e-10,
'd_convergence': 1e-10,
'pcm': True,
'pcm_scf_type': "total"
})
psi4.pcm_helper("""
Units = AU
Cavity {
Type = GePol
}
Medium {
SolverType = IEFPCM
Solvent = Water
Nonequilibrium = True
}
""")
psi4.core.set_num_threads(4)
scf_e, wfn = psi4.energy('scf', return_wfn=True)
# Run an ADC2 calculation with ptLR
state = adcc.adc2(wfn, n_singlets=5, conv_tol=1e-8, environment="ptlr")
print(state.describe())
