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# Psi4: an open-source quantum chemistry software package
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# Copyright (c) 2007-2021 The Psi4 Developers.
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# Psi4 is free software; you can redistribute it and/or modify
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from typing import Tuple
import numpy as np
from qcelemental import constants
from psi4 import core
from psi4.driver import p4util
from psi4.driver.p4util.exceptions import *
from psi4.driver.procrouting.dft import functionals, build_superfunctional_from_dictionary
from psi4.driver.procrouting.sapt import fisapt_proc
def scf_set_reference_local(name, is_dft=False):
"""
Figures out the correct SCF reference to set locally
"""
optstash = p4util.OptionsState(['SCF_TYPE'], ['SCF', 'REFERENCE'])
# Alter default algorithm
if not core.has_global_option_changed('SCF_TYPE'):
core.set_global_option('SCF_TYPE', 'DF')
# Alter reference name if needed
user_ref = core.get_option('SCF', 'REFERENCE')
sup = build_superfunctional_from_dictionary(functionals[name], 1, 1, True)[0]
if sup.needs_xc() or is_dft:
if (user_ref == 'RHF'):
core.set_local_option('SCF', 'REFERENCE', 'RKS')
elif (user_ref == 'UHF'):
core.set_local_option('SCF', 'REFERENCE', 'UKS')
elif (user_ref == 'ROHF'):
raise ValidationError('ROHF reference for DFT is not available.')
elif (user_ref == 'CUHF'):
raise ValidationError('CUHF reference for DFT is not available.')
# else we are doing HF and nothing needs to be overloaded
return optstash
def oeprop_validator(prop_list):
"""
Validations a list of OEProp computations. Throws if not found
"""
oeprop_methods = core.OEProp.valid_methods
if not len(prop_list):
raise ValidationError("OEProp: No properties specified!")
for prop in prop_list:
prop = prop.upper()
if 'MULTIPOLE(' in prop: continue
if prop not in oeprop_methods:
alt_method_name = p4util.text.find_approximate_string_matches(prop, oeprop_methods, 2)
alternatives = ""
if len(alt_method_name) > 0:
alternatives = " Did you mean? %s" % (" ".join(alt_method_name))
raise ValidationError("OEProp: Feature '%s' is not recognized. %s" % (prop, alternatives))
[docs]def check_iwl_file_from_scf_type(scf_type, wfn):
"""
Ensures that a IWL file has been written based on input SCF type.
"""
if scf_type in ['DF', 'DISK_DF', 'MEM_DF', 'CD', 'PK', 'DIRECT']:
mints = core.MintsHelper(wfn.basisset())
if core.get_global_option("RELATIVISTIC") in ["X2C", "DKH"]:
rel_bas = core.BasisSet.build(wfn.molecule(),
"BASIS_RELATIVISTIC",
core.get_option("SCF", "BASIS_RELATIVISTIC"),
"DECON",
core.get_global_option('BASIS'),
puream=wfn.basisset().has_puream())
mints.set_basisset('BASIS_RELATIVISTIC', rel_bas)
mints.set_print(1)
mints.integrals()
def check_non_symmetric_jk_density(name):
"""
Ensure non-symmetric density matrices are supported for the selected JK routine.
"""
scf_type = core.get_global_option('SCF_TYPE')
supp_jk_type = ['DF', 'DISK_DF', 'MEM_DF', 'CD', 'PK', 'DIRECT', 'OUT_OF_CORE']
supp_string = ', '.join(supp_jk_type[:-1]) + ', or ' + supp_jk_type[-1] + '.'
if scf_type not in supp_jk_type:
raise ValidationError("Method %s: Requires support for non-symmetric density matrices.\n"
" Please set SCF_TYPE to %s" % (name, supp_string))
def check_disk_df(name, optstash):
optstash.add_option(['SCF_TYPE'])
# Alter default algorithm
if not core.has_global_option_changed('SCF_TYPE') or core.get_global_option('SCF_TYPE') == "DF":
core.set_global_option('SCF_TYPE', 'DISK_DF')
core.print_out(f""" For method '{name}', SCF Algorithm Type (re)set to DISK_DF.\n""")
else:
if core.get_global_option('SCF_TYPE') == "MEM_DF":
raise ValidationError(
f" Method '{name}' requires SCF_TYPE = DISK_DF, please use SCF_TYPE = DF to automatically choose the correct DFJK implementation."
)
def print_ci_results(ciwfn, rname, scf_e, ci_e, print_opdm_no=False):
"""
Printing for all CI Wavefunctions
"""
# Print out energetics
core.print_out("\n ==> Energetics <==\n\n")
core.print_out(" SCF energy = %20.15f\n" % scf_e)
if "CI" in rname:
core.print_out(" Total CI energy = %20.15f\n" % ci_e)
elif "MP" in rname:
core.print_out(" Total MP energy = %20.15f\n" % ci_e)
elif "ZAPT" in rname:
core.print_out(" Total ZAPT energy = %20.15f\n" % ci_e)
else:
core.print_out(" Total MCSCF energy = %20.15f\n" % ci_e)
# Nothing to be done for ZAPT or MP
if ("MP" in rname) or ("ZAPT" in rname):
core.print_out("\n")
return
# Initial info
ci_nroots = core.get_option("DETCI", "NUM_ROOTS")
irrep_labels = ciwfn.molecule().irrep_labels()
# Grab the D-vector
dvec = ciwfn.D_vector()
dvec.init_io_files(True)
for root in range(ci_nroots):
core.print_out("\n ==> %s root %d information <==\n\n" % (rname, root))
# Print total energy
root_e = ciwfn.variable("CI ROOT %d TOTAL ENERGY" % (root))
core.print_out(" %s Root %d energy = %20.15f\n" % (rname, root, root_e))
# Print natural occupations
if print_opdm_no:
core.print_out("\n Active Space Natural occupation numbers:\n\n")
occs_list = []
r_opdm = ciwfn.get_opdm(root, root, "SUM", False)
for h in range(len(r_opdm.nph)):
if 0 in r_opdm.nph[h].shape:
continue
nocc, rot = np.linalg.eigh(r_opdm.nph[h])
for e in nocc:
occs_list.append((e, irrep_labels[h]))
occs_list.sort(key=lambda x: -x[0])
cnt = 0
for value, label in occs_list:
value, label = occs_list[cnt]
core.print_out(" %4s % 8.6f" % (label, value))
cnt += 1
if (cnt % 3) == 0:
core.print_out("\n")
if (cnt % 3):
core.print_out("\n")
# Print CIVector information
ciwfn.print_vector(dvec, root)
# True to keep the file
dvec.close_io_files(True)
def prepare_sapt_molecule(sapt_dimer: core.Molecule, sapt_basis: str) -> Tuple[core.Molecule, core.Molecule, core.Molecule]:
"""
Prepares a dimer molecule for a SAPT computations. Returns the dimer, monomerA, and monomerB.
"""
# Shifting to C1 so we need to copy the active molecule
sapt_dimer = sapt_dimer.clone()
if sapt_dimer.schoenflies_symbol() != 'c1':
core.print_out(' SAPT does not make use of molecular symmetry, further calculations in C1 point group.\n')
sapt_dimer.reset_point_group('c1')
sapt_dimer.fix_orientation(True)
sapt_dimer.fix_com(True)
sapt_dimer.update_geometry()
else:
sapt_dimer.update_geometry() # make sure since mol from wfn, kwarg, or P::e
sapt_dimer.fix_orientation(True)
sapt_dimer.fix_com(True)
nfrag = sapt_dimer.nfragments()
if nfrag == 3:
# Midbond case
if sapt_basis == 'monomer':
raise ValidationError("SAPT basis cannot both be monomer centered and have midbond functions.")
midbond = sapt_dimer.extract_subsets(3)
ztotal = 0
for n in range(midbond.natom()):
ztotal += midbond.Z(n)
if ztotal > 0:
raise ValidationError("SAPT third monomer must be a midbond function (all ghosts).")
ghosts = ([2, 3], [1, 3])
elif nfrag == 2:
# Classical dimer case
ghosts = (2, 1)
else:
raise ValidationError('SAPT requires active molecule to have 2 fragments, not %s.' % (nfrag))
if sapt_basis == 'dimer':
monomerA = sapt_dimer.extract_subsets(1, ghosts[0])
monomerA.set_name('monomerA')
monomerB = sapt_dimer.extract_subsets(2, ghosts[1])
monomerB.set_name('monomerB')
elif sapt_basis == 'monomer':
monomerA = sapt_dimer.extract_subsets(1)
monomerA.set_name('monomerA')
monomerB = sapt_dimer.extract_subsets(2)
monomerB.set_name('monomerB')
else:
raise ValidationError("SAPT basis %s not recognized" % sapt_basis)
return (sapt_dimer, monomerA, monomerB)
def sapt_empirical_dispersion(name, dimer_wfn, **kwargs):
sapt_dimer = dimer_wfn.molecule()
sapt_dimer, monomerA, monomerB = prepare_sapt_molecule(sapt_dimer, "dimer")
disp_name = name.split("-")[1]
# Get the names right between SAPT0 and FISAPT0
saptd_name = name.split('-')[0].upper()
if saptd_name == "SAPT0":
sapt0_name = "SAPT0"
else:
sapt0_name = "SAPT"
save_pair = (saptd_name == "FISAPT0")
from .proc import build_disp_functor
_, _disp_functor = build_disp_functor('hf-' + disp_name, restricted=True, save_pairwise_disp=save_pair, **kwargs)
## Dimer dispersion
dimer_disp_energy = _disp_functor.compute_energy(dimer_wfn.molecule(), dimer_wfn)
## Monomer dispersion
mon_disp_energy = _disp_functor.compute_energy(monomerA)
mon_disp_energy += _disp_functor.compute_energy(monomerB)
disp_interaction_energy = dimer_disp_energy - mon_disp_energy
core.set_variable(saptd_name + "-D DISP ENERGY", disp_interaction_energy)
core.set_variable("SAPT DISP ENERGY", disp_interaction_energy)
core.set_variable("DISPERSION CORRECTION ENERGY", disp_interaction_energy)
core.set_variable(saptd_name + "DISPERSION CORRECTION ENERGY", disp_interaction_energy)
## Set SAPT0-D3 variables
total = disp_interaction_energy
saptd_en = {}
saptd_en['DISP'] = disp_interaction_energy
for term in ['ELST', 'EXCH', 'IND']:
en = core.variable(' '.join([sapt0_name, term, 'ENERGY']))
saptd_en[term] = en
core.set_variable(' '.join([saptd_name + '-D', term, 'ENERGY']), en)
core.set_variable(' '.join(['SAPT', term, 'ENERGY']), en)
total += en
core.set_variable(saptd_name + '-D TOTAL ENERGY', total)
core.set_variable('SAPT TOTAL ENERGY', total)
core.set_variable('CURRENT ENERGY', total)
## Print Energy Summary
units = (1000.0, constants.hartree2kcalmol, constants.hartree2kJmol)
core.print_out(f" => {saptd_name +'-D'} Energy Summary <=\n")
core.print_out(" " + "-" * 104 + "\n")
core.print_out(
" %-25s % 16.8f [mEh] % 16.8f [kcal/mol] % 16.8f [kJ/mol]\n" %
("Electrostatics", saptd_en['ELST'] * units[0], saptd_en['ELST'] * units[1], saptd_en['ELST'] * units[2]))
core.print_out(" %-25s % 16.8f [mEh] % 16.8f [kcal/mol] % 16.8f [kJ/mol]\n" %
("Exchange", saptd_en['EXCH'] * units[0], saptd_en['EXCH'] * units[1], saptd_en['EXCH'] * units[2]))
core.print_out(" %-25s % 16.8f [mEh] % 16.8f [kcal/mol] % 16.8f [kJ/mol]\n" %
("Induction", saptd_en['IND'] * units[0], saptd_en['IND'] * units[1], saptd_en['IND'] * units[2]))
core.print_out(
" %-25s % 16.8f [mEh] % 16.8f [kcal/mol] % 16.8f [kJ/mol]\n" %
("Dispersion", saptd_en['DISP'] * units[0], saptd_en['DISP'] * units[1], saptd_en['DISP'] * units[2]))
core.print_out(" %-27s % 16.8f [mEh] % 16.8f [kcal/mol] % 16.8f [kJ/mol]\n" %
("Total " + saptd_name + "-D", total * units[0], total * units[1], total * units[2]))
core.print_out(" " + "-" * 104 + "\n")
if saptd_name == "FISAPT0":
pw_disp = dimer_wfn.variable("PAIRWISE DISPERSION CORRECTION ANALYSIS")
pw_disp.name = 'Empirical_Disp'
filepath = core.get_option("FISAPT", "FISAPT_FSAPT_FILEPATH")
fisapt_proc._drop(pw_disp, filepath)
return dimer_wfn
