# Copyright 2014-2020 The PySCF Developers. All Rights Reserved.
#
# Licensed under the Apache License, Version 2.0 (the "License");
# you may not use this file except in compliance with the License.
# You may obtain a copy of the License at
#
# http://www.apache.org/licenses/LICENSE-2.0
#
# Unless required by applicable law or agreed to in writing, software
# distributed under the License is distributed on an "AS IS" BASIS,
# WITHOUT WARRANTIES OR CONDITIONS OF ANY KIND, either express or implied.
# See the License for the specific language governing permissions and
# limitations under the License.
'''
Coupled Cluster
===============
Simple usage::
>>> from pyscf import gto, scf, cc
>>> mol = gto.M(atom='H 0 0 0; H 0 0 1')
>>> mf = scf.RHF(mol).run()
>>> cc.CCSD(mf).run()
:func:`cc.CCSD` returns an instance of CCSD class. Followings are parameters
to control CCSD calculation.
verbose : int
Print level. Default value equals to :class:`Mole.verbose`
max_memory : float or int
Allowed memory in MB. Default value equals to :class:`Mole.max_memory`
conv_tol : float
converge threshold. Default is 1e-7.
conv_tol_normt : float
converge threshold for norm(t1,t2). Default is 1e-5.
max_cycle : int
max number of iterations. Default is 50.
diis_space : int
DIIS space size. Default is 6.
diis_start_cycle : int
The step to start DIIS. Default is 0.
direct : bool
AO-direct CCSD. Default is False.
async_io : bool
Allow for asynchronous function execution. Default is True.
incore_complete : bool
Avoid all I/O. Default is False.
frozen : int or list
If integer is given, the inner-most orbitals are frozen from CC
amplitudes. Given the orbital indices (0-based) in a list, both
occupied and virtual orbitals can be frozen in CC calculation.
Saved results
converged : bool
CCSD converged or not
e_tot : float
Total CCSD energy (HF + correlation)
t1, t2 :
t1[i,a], t2[i,j,a,b] (i,j in occ, a,b in virt)
l1, l2 :
Lambda amplitudes l1[i,a], l2[i,j,a,b] (i,j in occ, a,b in virt)
'''
from pyscf.cc import ccsd
from pyscf.cc import ccsd_lambda
from pyscf.cc import ccsd_rdm
from pyscf.cc import addons
from pyscf.cc import rccsd
from pyscf.cc import uccsd
from pyscf.cc import gccsd
from pyscf.cc import eom_rccsd
from pyscf.cc import eom_uccsd
from pyscf.cc import eom_gccsd
from pyscf.cc import qcisd
from pyscf.cc import momgfccsd
from pyscf import scf
[docs]
def CCSD(mf, frozen=None, mo_coeff=None, mo_occ=None):
if isinstance(mf, scf.uhf.UHF):
return UCCSD(mf, frozen, mo_coeff, mo_occ)
elif isinstance(mf, scf.ghf.GHF):
return GCCSD(mf, frozen, mo_coeff, mo_occ)
else:
return RCCSD(mf, frozen, mo_coeff, mo_occ)
CCSD.__doc__ = ccsd.CCSD.__doc__
scf.hf.SCF.CCSD = CCSD
[docs]
def RCCSD(mf, frozen=None, mo_coeff=None, mo_occ=None):
import numpy
from pyscf import lib
from pyscf.soscf import newton_ah
from pyscf.cc import dfccsd
if isinstance(mf, scf.uhf.UHF):
raise RuntimeError('RCCSD cannot be used with UHF method.')
elif isinstance(mf, scf.rohf.ROHF):
lib.logger.warn(mf, 'RCCSD method does not support ROHF method. ROHF object '
'is converted to UHF object and UCCSD method is called.')
mf = scf.addons.convert_to_uhf(mf)
return UCCSD(mf, frozen, mo_coeff, mo_occ)
if isinstance(mf, newton_ah._CIAH_SOSCF) or not isinstance(mf, scf.hf.RHF):
mf = scf.addons.convert_to_rhf(mf)
if getattr(mf, 'with_df', None):
return dfccsd.RCCSD(mf, frozen, mo_coeff, mo_occ)
elif numpy.iscomplexobj(mo_coeff) or numpy.iscomplexobj(mf.mo_coeff):
return rccsd.RCCSD(mf, frozen, mo_coeff, mo_occ)
else:
return ccsd.CCSD(mf, frozen, mo_coeff, mo_occ)
RCCSD.__doc__ = ccsd.CCSD.__doc__
[docs]
def UCCSD(mf, frozen=None, mo_coeff=None, mo_occ=None):
from pyscf.soscf import newton_ah
if isinstance(mf, newton_ah._CIAH_SOSCF) or not isinstance(mf, scf.uhf.UHF):
mf = scf.addons.convert_to_uhf(mf)
if getattr(mf, 'with_df', None):
# TODO: DF-UCCSD with memory-efficient particle-particle ladder,
# similar to dfccsd.RCCSD
return uccsd.UCCSD(mf, frozen, mo_coeff, mo_occ)
else:
return uccsd.UCCSD(mf, frozen, mo_coeff, mo_occ)
UCCSD.__doc__ = uccsd.UCCSD.__doc__
[docs]
def GCCSD(mf, frozen=None, mo_coeff=None, mo_occ=None):
from pyscf.soscf import newton_ah
if isinstance(mf, newton_ah._CIAH_SOSCF) or not isinstance(mf, scf.ghf.GHF):
mf = scf.addons.convert_to_ghf(mf)
if getattr(mf, 'with_df', None):
raise NotImplementedError('DF-GCCSD')
else:
return gccsd.GCCSD(mf, frozen, mo_coeff, mo_occ)
GCCSD.__doc__ = gccsd.GCCSD.__doc__
[docs]
def QCISD(mf, frozen=None, mo_coeff=None, mo_occ=None):
if isinstance(mf, scf.uhf.UHF):
raise NotImplementedError
elif isinstance(mf, scf.ghf.GHF):
raise NotImplementedError
else:
return RQCISD(mf, frozen, mo_coeff, mo_occ)
QCISD.__doc__ = qcisd.QCISD.__doc__
scf.hf.SCF.QCISD = QCISD
[docs]
def RQCISD(mf, frozen=None, mo_coeff=None, mo_occ=None):
import numpy
from pyscf import lib
from pyscf.soscf import newton_ah
if isinstance(mf, scf.uhf.UHF):
raise RuntimeError('RQCISD cannot be used with UHF method.')
elif isinstance(mf, scf.rohf.ROHF):
lib.logger.warn(mf, 'RQCISD method does not support ROHF method. ROHF object '
'is converted to UHF object and UQCISD method is called.')
mf = scf.addons.convert_to_uhf(mf)
raise NotImplementedError
if isinstance(mf, newton_ah._CIAH_SOSCF) or not isinstance(mf, scf.hf.RHF):
mf = scf.addons.convert_to_rhf(mf)
elif numpy.iscomplexobj(mo_coeff) or numpy.iscomplexobj(mf.mo_coeff):
raise NotImplementedError
else:
return qcisd.QCISD(mf, frozen, mo_coeff, mo_occ)
RQCISD.__doc__ = qcisd.QCISD.__doc__
[docs]
def FNOCCSD(mf, thresh=1e-6, pct_occ=None, nvir_act=None, frozen=None):
"""Frozen natural orbital CCSD
Attributes:
thresh : float
Threshold on NO occupation numbers. Default is 1e-6 (very conservative).
pct_occ : float
Percentage of total occupation number. Default is None. If present, overrides `thresh`.
nvir_act : int
Number of virtual NOs to keep. Default is None. If present, overrides `thresh` and `pct_occ`.
"""
import numpy
if frozen is None:
frozenocc = 0
else:
assert(isinstance(frozen, (int,numpy.int64)))
frozenocc = frozen
from pyscf import mp
pt = mp.MP2(mf).set(verbose=0).run()
frozen, no_coeff = pt.make_fno(thresh=thresh, pct_occ=pct_occ, nvir_act=nvir_act)
frozen = numpy.hstack([numpy.arange(frozenocc),frozen])
if len(frozen) == 0: frozen = None
pt_no = mp.MP2(mf, frozen=frozen, mo_coeff=no_coeff).set(verbose=0).run()
mycc = CCSD(mf, frozen=frozen, mo_coeff=no_coeff)
mycc.delta_emp2 = pt.e_corr - pt_no.e_corr
from pyscf.lib import logger
def _finalize(self):
'''Hook for dumping results and clearing up the object.'''
if self.converged:
logger.info(self, 'FNO-%s converged', self.__class__.__name__)
else:
logger.note(self, 'FNO-%s not converged', self.__class__.__name__)
logger.note(self, 'E(FNO-%s) = %.16g E_corr = %.16g',
self.__class__.__name__, self.e_tot, self.e_corr)
logger.note(self, 'E(FNO-%s+delta-MP2) = %.16g E_corr = %.16g',
self.__class__.__name__, self.e_tot+self.delta_emp2,
self.e_corr+self.delta_emp2)
return self
mycc._finalize = _finalize.__get__(mycc, mycc.__class__)
return mycc
MomGFCCSD = momgfccsd.MomGFCCSD