#!/usr/bin/env python
# Copyright 2014-2021 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>
#
import numpy
from pyscf import lib
from pyscf.cc import gccsd_rdm
def _gamma1_intermediates(mycc, t1, t2, l1, l2, eris=None):
doo, dov, dvo, dvv = gccsd_rdm._gamma1_intermediates(mycc, t1, t2, l1, l2)
if eris is None: eris = mycc.ao2mo()
nocc, nvir = t1.shape
bcei = numpy.asarray(eris.ovvv).conj().transpose(3,2,1,0)
majk = numpy.asarray(eris.ooov).conj().transpose(2,3,0,1)
bcjk = numpy.asarray(eris.oovv).conj().transpose(2,3,0,1)
mo_e = eris.mo_energy
eia = mo_e[:nocc,None] - mo_e[nocc:]
d3 = lib.direct_sum('ia+jb+kc->ijkabc', eia, eia, eia)
t3c =(numpy.einsum('jkae,bcei->ijkabc', t2, bcei) -
numpy.einsum('imbc,majk->ijkabc', t2, majk))
t3c = t3c - t3c.transpose(0,1,2,4,3,5) - t3c.transpose(0,1,2,5,4,3)
t3c = t3c - t3c.transpose(1,0,2,3,4,5) - t3c.transpose(2,1,0,3,4,5)
t3c /= d3
t3d = numpy.einsum('ia,bcjk->ijkabc', t1, bcjk)
t3d += numpy.einsum('ai,jkbc->ijkabc', eris.fock[nocc:,:nocc], t2)
t3d = t3d - t3d.transpose(0,1,2,4,3,5) - t3d.transpose(0,1,2,5,4,3)
t3d = t3d - t3d.transpose(1,0,2,3,4,5) - t3d.transpose(2,1,0,3,4,5)
t3d /= d3
goo = numpy.einsum('iklabc,jklabc->ij', (t3c+t3d).conj(), t3c) * (1./12)
gvv = numpy.einsum('ijkacd,ijkbcd->ab', t3c+t3d, t3c.conj()) * (1./12)
doo[numpy.diag_indices(nocc)] -= goo.diagonal()
dvv[numpy.diag_indices(nvir)] += gvv.diagonal()
dvo += numpy.einsum('ijab,ijkabc->ck', t2.conj(), t3c) * (1./4)
return doo, dov, dvo, dvv
# gamma2 intermediates in Chemist's notation
def _gamma2_intermediates(mycc, t1, t2, l1, l2, eris=None):
dovov, dvvvv, doooo, doovv, dovvo, dvvov, dovvv, dooov = \
gccsd_rdm._gamma2_intermediates(mycc, t1, t2, l1, l2)
if eris is None: eris = mycc.ao2mo()
nocc, nvir = t1.shape
bcei = numpy.asarray(eris.ovvv).conj().transpose(3,2,1,0)
majk = numpy.asarray(eris.ooov).conj().transpose(2,3,0,1)
bcjk = numpy.asarray(eris.oovv).conj().transpose(2,3,0,1)
mo_e = eris.mo_energy
eia = mo_e[:nocc,None] - mo_e[nocc:]
d3 = lib.direct_sum('ia+jb+kc->ijkabc', eia, eia, eia)
t3c =(numpy.einsum('jkae,bcei->ijkabc', t2, bcei) -
numpy.einsum('imbc,majk->ijkabc', t2, majk))
t3c = t3c - t3c.transpose(0,1,2,4,3,5) - t3c.transpose(0,1,2,5,4,3)
t3c = t3c - t3c.transpose(1,0,2,3,4,5) - t3c.transpose(2,1,0,3,4,5)
t3c /= d3
t3d = numpy.einsum('ia,bcjk->ijkabc', t1, bcjk)
t3d += numpy.einsum('ai,jkbc->ijkabc', eris.fock[nocc:,:nocc], t2)
t3d = t3d - t3d.transpose(0,1,2,4,3,5) - t3d.transpose(0,1,2,5,4,3)
t3d = t3d - t3d.transpose(1,0,2,3,4,5) - t3d.transpose(2,1,0,3,4,5)
t3d /= d3
goovv = numpy.einsum('kc,ijkabc->ijab', t1.conj(), t3c).conj() * (1./4)
dovov += goovv.transpose(0,2,1,3) - goovv.transpose(0,3,1,2)
m3 = t3c * 2 + t3d
# *(1/8) instead of (1/4) because ooov appears 4 times in the 2pdm tensor due
# to symmetrization, and its contribution is scaled by 1/2 in Tr(H,2pdm)
gooov = numpy.einsum('imbc,ijkabc->jkma', t2, m3.conj()) * (1./8)
dooov -= gooov.transpose(0,2,1,3) - gooov.transpose(1,2,0,3)
govvv = numpy.einsum('jkae,ijkabc->iecb', t2, m3.conj()) * (1./8)
dovvv += govvv.transpose(0,2,1,3) - govvv.transpose(0,3,1,2)
return dovov, dvvvv, doooo, doovv, dovvo, dvvov, dovvv, dooov
[docs]
def make_rdm1(mycc, t1, t2, l1, l2, eris=None, ao_repr=False):
d1 = _gamma1_intermediates(mycc, t1, t2, l1, l2, eris)
return gccsd_rdm._make_rdm1(mycc, d1, True, ao_repr=ao_repr)
# rdm2 in Chemist's notation
[docs]
def make_rdm2(mycc, t1, t2, l1, l2, eris=None):
d1 = _gamma1_intermediates(mycc, t1, t2, l1, l2, eris)
d2 = _gamma2_intermediates(mycc, t1, t2, l1, l2, eris)
return gccsd_rdm._make_rdm2(mycc, d1, d2, True, True)
if __name__ == '__main__':
from functools import reduce
from pyscf import gto
from pyscf import scf
from pyscf import ao2mo
from pyscf import cc
mol = gto.Mole()
mol.atom = [
[8 , (0. , 0. , 0.)],
[1 , (0. , -.957 , .587)],
[1 , (0.2, .757 , .487)]]
mol.basis = '631g'
mol.build()
mf0 = mf = scf.RHF(mol).run(conv_tol=1.)
mf = scf.addons.convert_to_ghf(mf)
from pyscf.cc import ccsd_t_lambda_slow as ccsd_t_lambda
from pyscf.cc import ccsd_t_rdm_slow as ccsd_t_rdm
mycc0 = cc.CCSD(mf0)
eris0 = mycc0.ao2mo()
mycc0.kernel(eris=eris0)
t1 = mycc0.t1
t2 = mycc0.t2
imds = ccsd_t_lambda.make_intermediates(mycc0, t1, t2, eris0)
l1, l2 = ccsd_t_lambda.update_lambda(mycc0, t1, t2, t1, t2, eris0, imds)
dm1ref = ccsd_t_rdm.make_rdm1(mycc0, t1, t2, l1, l2, eris0)
dm2ref = ccsd_t_rdm.make_rdm2(mycc0, t1, t2, l1, l2, eris0)
mycc = cc.GCCSD(mf)
eris = mycc.ao2mo()
t1 = mycc.spatial2spin(t1, mycc.mo_coeff.orbspin)
t2 = mycc.spatial2spin(t2, mycc.mo_coeff.orbspin)
l1 = mycc.spatial2spin(l1, mycc.mo_coeff.orbspin)
l2 = mycc.spatial2spin(l2, mycc.mo_coeff.orbspin)
gdm1 = make_rdm1(mycc, t1, t2, l1, l2, eris)
gdm2 = make_rdm2(mycc, t1, t2, l1, l2, eris)
idxa = numpy.where(mycc.mo_coeff.orbspin == 0)[0]
idxb = numpy.where(mycc.mo_coeff.orbspin == 1)[0]
trdm1 = gdm1[idxa[:,None],idxa]
trdm1+= gdm1[idxb[:,None],idxb]
trdm2 = gdm2[idxa[:,None,None,None],idxa[:,None,None],idxa[:,None],idxa]
trdm2+= gdm2[idxb[:,None,None,None],idxb[:,None,None],idxb[:,None],idxb]
dm2ab = gdm2[idxa[:,None,None,None],idxa[:,None,None],idxb[:,None],idxb]
trdm2+= dm2ab
trdm2+= dm2ab.transpose(2,3,0,1)
print(abs(trdm1 - dm1ref).max())
print(abs(trdm2 - dm2ref).max())
mol = gto.Mole()
mol.atom = [
[8 , (0. , 0. , 0.)],
[1 , (0. , -0.757 , 0.587)],
[1 , (0. , 0.757 , 0.587)]]
mol.basis = '631g'
mol.spin = 2
mol.charge = 2
mol.build()
mf0 = mf = scf.UHF(mol).run(conv_tol=1)
mf = scf.addons.convert_to_ghf(mf)
from pyscf.cc import uccsd_t_lambda
from pyscf.cc import uccsd_t_rdm
mycc0 = cc.UCCSD(mf0)
eris0 = mycc0.ao2mo()
mycc0.kernel(eris=eris0)
t1 = mycc0.t1
t2 = mycc0.t2
imds = uccsd_t_lambda.make_intermediates(mycc0, t1, t2, eris0)
l1, l2 = uccsd_t_lambda.update_lambda(mycc0, t1, t2, t1, t2, eris0, imds)
dm1ref = uccsd_t_rdm.make_rdm1(mycc0, t1, t2, l1, l2, eris0)
dm2ref = uccsd_t_rdm.make_rdm2(mycc0, t1, t2, l1, l2, eris0)
mycc = cc.GCCSD(mf)
eris = mycc.ao2mo()
t1 = mycc.spatial2spin(t1, mycc.mo_coeff.orbspin)
t2 = mycc.spatial2spin(t2, mycc.mo_coeff.orbspin)
l1 = mycc.spatial2spin(l1, mycc.mo_coeff.orbspin)
l2 = mycc.spatial2spin(l2, mycc.mo_coeff.orbspin)
gdm1 = make_rdm1(mycc, t1, t2, l1, l2, eris)
gdm2 = make_rdm2(mycc, t1, t2, l1, l2, eris)
idxa = numpy.where(mycc.mo_coeff.orbspin == 0)[0]
idxb = numpy.where(mycc.mo_coeff.orbspin == 1)[0]
print(abs(dm1ref[0] - gdm1[idxa[:,None],idxa]).max())
print(abs(dm1ref[1] - gdm1[idxb[:,None],idxb]).max())
print(abs(dm2ref[0] - gdm2[idxa[:,None,None,None],idxa[:,None,None],idxa[:,None],idxa]).max())
print(abs(dm2ref[1] - gdm2[idxa[:,None,None,None],idxa[:,None,None],idxb[:,None],idxb]).max())
print(abs(dm2ref[2] - gdm2[idxb[:,None,None,None],idxb[:,None,None],idxb[:,None],idxb]).max())
ecc, t1, t2 = mycc.kernel(eris=eris)
e3ref = mycc.e_tot + mycc.ccsd_t()
l1, l2 = mycc.solve_lambda(eris=eris)
dm1 = make_rdm1(mycc, t1, t2, l1, l2, eris=eris)
dm2 = make_rdm2(mycc, t1, t2, l1, l2, eris=eris)
nao = mol.nao_nr()
mo_a = mf.mo_coeff[:nao]
mo_b = mf.mo_coeff[nao:]
nmo = mo_a.shape[1]
eri = ao2mo.kernel(mf._eri, mo_a+mo_b, compact=False).reshape([nmo]*4)
orbspin = mf.mo_coeff.orbspin
sym_forbid = (orbspin[:,None] != orbspin)
eri[sym_forbid,:,:] = 0
eri[:,:,sym_forbid] = 0
hcore = scf.RHF(mol).get_hcore()
h1 = reduce(numpy.dot, (mo_a.T.conj(), hcore, mo_a))
h1+= reduce(numpy.dot, (mo_b.T.conj(), hcore, mo_b))
e3 = numpy.einsum('ij,ji', h1, dm1)
e3+= numpy.einsum('ijkl,ijkl', eri, dm2) * .5
e3+= mol.energy_nuc()
print(e3 - e3ref)