#!/usr/bin/env python
# Copyright 2014-2019 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.
#
# Author: Qiming Sun <osirpt.sun@gmail.com>
#
from pyscf import lib
from pyscf.cc import uccsd_t_rdm
from pyscf.grad import uccsd as uccsd_grad
# Only works with canonical orbitals
[docs]
def grad_elec(cc_grad, t1=None, t2=None, l1=None, l2=None, eris=None, atmlst=None,
verbose=lib.logger.INFO):
mycc = cc_grad.base
if t1 is None: t1 = mycc.t1
if t2 is None: t2 = mycc.t2
if l1 is None: l1 = mycc.l1
if l2 is None: l2 = mycc.l2
if eris is None: eris = mycc.ao2mo()
d1 = uccsd_t_rdm._gamma1_intermediates(mycc, t1, t2, l1, l2, eris,
for_grad=True)
fd2intermediate = lib.H5TmpFile()
d2 = uccsd_t_rdm._gamma2_outcore(mycc, t1, t2, l1, l2, eris,
fd2intermediate, True)
cc_grad = uccsd_grad.Gradients(mycc)
de = uccsd_grad.grad_elec(cc_grad, t1, t2, l1, l2, eris, atmlst,
d1, d2, verbose)
return de
[docs]
class Gradients(uccsd_grad.Gradients):
grad_elec = grad_elec
if __name__ == '__main__':
from pyscf import gto
from pyscf import scf
from pyscf import cc
from pyscf.cc import uccsd_t
from pyscf.cc import uccsd_t_lambda
mol = gto.M(
verbose = 0,
atom = [
["O" , (0. , 0. , 0. )],
[1 , (0. ,-0.757 ,-0.587)],
[1 , (0. , 0.757 ,-0.587)]],
basis = '631g',
spin=2,
)
mf = scf.UHF(mol)
mf.conv_tol = 1e-14
ehf = mf.scf()
mycc = cc.UCCSD(mf)
mycc.conv_tol = 1e-10
mycc.conv_tol_normt = 1e-10
ecc, t1, t2 = mycc.kernel()
eris = mycc.ao2mo()
e3ref = uccsd_t.kernel(mycc, eris, t1, t2)
print(ehf+ecc+e3ref)
conv, l1, l2 = uccsd_t_lambda.kernel(mycc, eris, t1, t2)
g1 = Gradients(mycc).kernel(t1, t2, l1, l2, eris=eris)
print(g1)
myccs = mycc.as_scanner()
mol.atom[0] = ["O" , (0., 0., 0.001)]
mol.build(0, 0)
e1 = myccs(mol)
e1 += myccs.ccsd_t()
mol.atom[0] = ["O" , (0., 0.,-0.001)]
mol.build(0, 0)
e2 = myccs(mol)
e2 += myccs.ccsd_t()
print(g1[0,2], (e1-e2)/0.002*lib.param.BOHR)
#O 0. 0.0000000 -0.1480942
#H 0. 0.1122898 0.0740461
#H 0. -0.1122898 0.0740461
mol = gto.M(
verbose = 0,
atom = '''
H -1.90779510 0.92319522 0.08700656
H -1.08388168 -1.61405643 -0.07315086
H 2.02822318 -0.61402169 0.09396693
H 0.96345360 1.30488291 -0.10782263
''',
unit='bohr',
basis = '631g')
mf = scf.UHF(mol)
mf.conv_tol = 1e-14
ehf0 = mf.scf()
mycc = cc.UCCSD(mf)
mycc.conv_tol = 1e-10
mycc.conv_tol_normt = 1e-10
ecc, t1, t2 = mycc.kernel()
eris = mycc.ao2mo()
e3ref = uccsd_t.kernel(mycc, eris, t1, t2)
print(ehf0+ecc+e3ref)
eris = mycc.ao2mo(mf.mo_coeff)
conv, l1, l2 = uccsd_t_lambda.kernel(mycc, eris, t1, t2)
g1 = Gradients(mycc).kernel(t1, t2, l1, l2, eris=eris)
print(g1)
myccs = mycc.as_scanner()
mol.atom = '''
H -1.90679510 0.92319522 0.08700656
H -1.08388168 -1.61405643 -0.07315086
H 2.02822318 -0.61402169 0.09396693
H 0.96345360 1.30488291 -0.10782263
'''
mol.build(0, 0)
e1 = myccs(mol)
e1 += myccs.ccsd_t()
mol.atom = '''
H -1.90879510 0.92319522 0.08700656
H -1.08388168 -1.61405643 -0.07315086
H 2.02822318 -0.61402169 0.09396693
H 0.96345360 1.30488291 -0.10782263
'''
mol.build(0, 0)
e2 = myccs(mol)
e2 += myccs.ccsd_t()
# FIXME: disagreements between analytical value and finite difference value
print(g1[0,0], (e1-e2)/0.002)
#CCSD
#H 0.0113620114 0.0664344363 0.0029855587
#H 0.0528858926 -0.0483942979 -0.0033960631
#H 0.0109676543 -0.0827248466 0.0074005299
#H -0.0752155583 0.0646847082 -0.0069900255
#
#CCSD(T) gradient:
#
#H 0.0112264011 0.0658917731 0.0029936671
#H 0.0525667206 -0.0481602008 -0.0033751503
#H 0.0107197424 -0.0823677005 0.0073804163
#H -0.0745128642 0.0646361282 -0.0069989330
