#!/usr/bin/env python
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# Licensed under the Apache License, Version 2.0 (the "License");
# you may not use this file except in compliance with the License.
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# http://www.apache.org/licenses/LICENSE-2.0
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import numpy as np
from pyscf import lib
from pyscf.lib import logger
#einsum = np.einsum
einsum = lib.einsum
# Ref: Gauss and Stanton, J. Chem. Phys. 103, 3561 (1995) Table III
# Section (a)
[docs]
def make_tau(t2, t1a, t1b, fac=1, out=None):
t1t1 = einsum('ia,jb->ijab', fac*0.5*t1a, t1b)
t1t1 = t1t1 - t1t1.transpose(1,0,2,3)
tau1 = t1t1 - t1t1.transpose(0,1,3,2)
tau1 += t2
return tau1
[docs]
def cc_Fvv(t1, t2, eris):
nocc, nvir = t1.shape
fov = eris.fock[:nocc,nocc:]
fvv = eris.fock[nocc:,nocc:]
eris_vovv = np.asarray(eris.ovvv).transpose(1,0,3,2)
tau_tilde = make_tau(t2, t1, t1,fac=0.5)
Fae = fvv - 0.5*einsum('me,ma->ae',fov, t1)
Fae += einsum('mf,amef->ae', t1, eris_vovv)
Fae -= 0.5*einsum('mnaf,mnef->ae', tau_tilde, eris.oovv)
return Fae
[docs]
def cc_Foo(t1, t2, eris):
nocc, nvir = t1.shape
fov = eris.fock[:nocc,nocc:]
foo = eris.fock[:nocc,:nocc]
tau_tilde = make_tau(t2, t1, t1,fac=0.5)
Fmi = ( foo + 0.5*einsum('me,ie->mi',fov, t1)
+ einsum('ne,mnie->mi', t1, eris.ooov)
+ 0.5*einsum('inef,mnef->mi', tau_tilde, eris.oovv) )
return Fmi
[docs]
def cc_Fov(t1, t2, eris):
nocc, nvir = t1.shape
fov = eris.fock[:nocc,nocc:]
Fme = fov + einsum('nf,mnef->me', t1, eris.oovv)
return Fme
[docs]
def cc_Woooo(t1, t2, eris):
tau = make_tau(t2, t1, t1)
tmp = einsum('je,mnie->mnij', t1, eris.ooov)
Wmnij = eris.oooo + tmp - tmp.transpose(0,1,3,2)
Wmnij += 0.25*einsum('ijef,mnef->mnij', tau, eris.oovv)
return Wmnij
[docs]
def cc_Wvvvv(t1, t2, eris):
tau = make_tau(t2, t1, t1)
eris_ovvv = np.asarray(eris.ovvv)
tmp = einsum('mb,mafe->bafe', t1, eris_ovvv)
Wabef = np.asarray(eris.vvvv) - tmp + tmp.transpose(1,0,2,3)
Wabef += einsum('mnab,mnef->abef', tau, 0.25*np.asarray(eris.oovv))
return Wabef
[docs]
def cc_Wovvo(t1, t2, eris):
eris_ovvo = -np.asarray(eris.ovov).transpose(0,1,3,2)
eris_oovo = -np.asarray(eris.ooov).transpose(0,1,3,2)
Wmbej = einsum('jf,mbef->mbej', t1, eris.ovvv)
Wmbej -= einsum('nb,mnej->mbej', t1, eris_oovo)
Wmbej -= 0.5*einsum('jnfb,mnef->mbej', t2, eris.oovv)
Wmbej -= einsum('jf,nb,mnef->mbej', t1, t1, eris.oovv)
Wmbej += eris_ovvo
return Wmbej
### Section (b)
[docs]
def Fvv(t1, t2, eris):
ccFov = cc_Fov(t1, t2, eris)
Fae = cc_Fvv(t1, t2, eris) - 0.5*einsum('ma,me->ae', t1,ccFov)
return Fae
[docs]
def Foo(t1, t2, eris):
ccFov = cc_Fov(t1, t2, eris)
Fmi = cc_Foo(t1, t2, eris) + 0.5*einsum('ie,me->mi', t1,ccFov)
return Fmi
[docs]
def Fov(t1, t2, eris):
Fme = cc_Fov(t1, t2, eris)
return Fme
[docs]
def Woooo(t1, t2, eris):
tau = make_tau(t2, t1, t1)
Wmnij = 0.25*einsum('ijef,mnef->mnij', tau, eris.oovv)
Wmnij += cc_Woooo(t1, t2, eris)
return Wmnij
[docs]
def Wvvvv(t1, t2, eris):
tau = make_tau(t2, t1, t1)
Wabef = cc_Wvvvv(t1, t2, eris)
Wabef += einsum('mnab,mnef->abef', tau, .25*np.asarray(eris.oovv))
return Wabef
[docs]
def Wovvo(t1, t2, eris):
Wmbej = -0.5*einsum('jnfb,mnef->mbej', t2, eris.oovv)
Wmbej += cc_Wovvo(t1, t2, eris)
return Wmbej
[docs]
def Wooov(t1, t2, eris):
Wmnie = einsum('if,mnfe->mnie', t1, eris.oovv)
Wmnie += eris.ooov
return Wmnie
[docs]
def Wvovv(t1, t2, eris):
Wamef = einsum('na,nmef->amef', -t1, eris.oovv)
Wamef -= np.asarray(eris.ovvv).transpose(1,0,2,3)
return Wamef
[docs]
def Wovoo(t1, t2, eris):
eris_ovvo = -np.asarray(eris.ovov).transpose(0,1,3,2)
tmp1 = einsum('mnie,jnbe->mbij', eris.ooov, t2)
tmp2 = einsum('ie,mbej->mbij', t1, eris_ovvo)
tmp2 -= einsum('ie,njbf,mnef->mbij', t1, t2, eris.oovv)
FFov = Fov(t1, t2, eris)
WWoooo = Woooo(t1, t2, eris)
tau = make_tau(t2, t1, t1)
Wmbij = einsum('me,ijbe->mbij', -FFov, t2)
Wmbij -= einsum('nb,mnij->mbij', t1, WWoooo)
Wmbij += 0.5 * einsum('mbef,ijef->mbij', eris.ovvv, tau)
Wmbij += tmp1 - tmp1.transpose(0,1,3,2)
Wmbij += tmp2 - tmp2.transpose(0,1,3,2)
Wmbij += np.asarray(eris.ooov).conj().transpose(2,3,0,1)
return Wmbij
[docs]
def Wvvvo(t1, t2, eris, _Wvvvv=None):
eris_ovvo = -np.asarray(eris.ovov).transpose(0,1,3,2)
eris_vvvo = -np.asarray(eris.ovvv).transpose(2,3,1,0).conj()
eris_oovo = -np.asarray(eris.ooov).transpose(0,1,3,2)
tmp1 = einsum('mbef,miaf->abei', eris.ovvv, t2)
tmp2 = einsum('ma,mbei->abei', t1, eris_ovvo)
tmp2 -= einsum('ma,nibf,mnef->abei', t1, t2, eris.oovv)
FFov = Fov(t1, t2, eris)
tau = make_tau(t2, t1, t1)
Wabei = 0.5 * einsum('mnei,mnab->abei', eris_oovo, tau)
Wabei -= einsum('me,miab->abei', FFov, t2)
Wabei += eris_vvvo
Wabei -= tmp1 - tmp1.transpose(1,0,2,3)
Wabei -= tmp2 - tmp2.transpose(1,0,2,3)
nocc,nvir = t1.shape
if _Wvvvv is None:
_Wvvvv = Wvvvv(t1, t2, eris)
Wabei += einsum('abef,if->abei', _Wvvvv, t1)
return Wabei
########################################
# T3[2] related contributions to T1/T2
########################################
[docs]
def get_t3p2_imds_slow(cc, t1, t2, eris=None, t3p2_ip_out=None, t3p2_ea_out=None):
"""Calculates T1, T2 amplitudes corrected by second-order T3 contribution
and intermediates used in IP/EA-CCSD(T)a
Args:
cc (:obj:`GCCSD`):
Object containing coupled-cluster results.
t1 (:obj:`ndarray`):
T1 amplitudes.
t2 (:obj:`ndarray`):
T2 amplitudes from which the T3[2] amplitudes are formed.
eris (:obj:`_PhysicistsERIs`):
Antisymmetrized electron-repulsion integrals in physicist's notation.
t3p2_ip_out (:obj:`ndarray`):
Store results of the intermediate used in IP-EOM-CCSD(T)a.
t3p2_ea_out (:obj:`ndarray`):
Store results of the intermediate used in EA-EOM-CCSD(T)a.
Returns:
delta_ccsd (float):
Difference of perturbed and unperturbed CCSD ground-state energy,
energy(T1 + T1[2], T2 + T2[2]) - energy(T1, T2)
pt1 (:obj:`ndarray`):
Perturbatively corrected T1 amplitudes.
pt2 (:obj:`ndarray`):
Perturbatively corrected T2 amplitudes.
Reference:
D. A. Matthews, J. F. Stanton "A new approach to approximate..."
JCP 145, 124102 (2016); DOI:10.1063/1.4962910, Equation 14
Shavitt and Bartlett "Many-body Methods in Physics and Chemistry"
2009, Equation 10.33
"""
if eris is None:
eris = cc.ao2mo()
fock = eris.fock
nocc, nvir = t1.shape
fov = fock[:nocc, nocc:]
#foo = fock[:nocc, :nocc].diagonal()
#fvv = fock[nocc:, nocc:].diagonal()
mo_e_o = eris.mo_energy[:nocc]
mo_e_v = eris.mo_energy[nocc:]
oovv = np.asarray(eris.oovv)
ovvv = np.asarray(eris.ovvv)
ooov = np.asarray(eris.ooov)
oovv = np.asarray(eris.oovv)
vooo = np.asarray(ooov).conj().transpose(3, 2, 1, 0)
vvvo = np.asarray(ovvv).conj().transpose(3, 2, 1, 0)
ccsd_energy = cc.energy(t1, t2, eris)
dtype = np.result_type(t1, t2)
if np.issubdtype(dtype, np.dtype(complex).type):
logger.error(cc, 't3p2 imds has not been strictly checked for use with complex integrals')
if t3p2_ip_out is None:
t3p2_ip_out = np.zeros((nocc,nvir,nocc,nocc), dtype=dtype)
Wmcik = t3p2_ip_out
if t3p2_ea_out is None:
t3p2_ea_out = np.zeros((nvir,nvir,nvir,nocc), dtype=dtype)
Wacek = t3p2_ea_out
tmp_t3 = lib.einsum('bcdk,ijad->ijkabc', vvvo, t2)
tmp_t3 -= lib.einsum('cmkj,imab->ijkabc', vooo, t2)
# P(ijk)
tmp_t3 = (tmp_t3 + tmp_t3.transpose(1, 2, 0, 3, 4, 5) +
tmp_t3.transpose(2, 0, 1, 3, 4, 5))
# P(abc)
tmp_t3 = (tmp_t3 + tmp_t3.transpose(0, 1, 2, 4, 5, 3) +
tmp_t3.transpose(0, 1, 2, 5, 3, 4))
eia = mo_e_o[:, None] - mo_e_v[None, :]
eijab = eia[:, None, :, None] + eia[None, :, None, :]
eijkabc = eijab[:, :, None, :, :, None] + eia[None, None, :, None, None, :]
tmp_t3 /= eijkabc
pt1 = 0.25 * lib.einsum('mnef,imnaef->ia', oovv, tmp_t3)
pt2 = lib.einsum('ijmabe,me->ijab', tmp_t3, fov)
tmp2 = ovvv - 0.0*lib.einsum('nmef,nb->mbfe', oovv, t1)
tmp = lib.einsum('ijmaef,mbfe->ijab', tmp_t3, tmp2)
tmp = tmp - tmp.transpose(0, 1, 3, 2) # P(ab)
tmp *= 0.5
pt2 = pt2 + tmp
tmp2 = ooov + 0.0*lib.einsum('mnef,jf->nmje', oovv, t1)
tmp = lib.einsum('inmabe,nmje->ijab', tmp_t3, tmp2)
tmp *= -0.5
tmp = tmp - tmp.transpose(1, 0, 2, 3) # P(ij)
pt2 = pt2 + tmp
eia = mo_e_o[:, None] - mo_e_v[None, :]
eijab = eia[:, None, :, None] + eia[None, :, None, :]
pt1 /= eia
pt2 /= eijab
pt1 = pt1 + t1
pt2 = pt2 + t2
Wmcik += 0.5*lib.einsum('ijkabc,mjab->mcik', tmp_t3, oovv)
Wacek += -0.5*lib.einsum('ijkabc,ijeb->acek', tmp_t3, oovv)
delta_ccsd_energy = cc.energy(pt1, pt2, eris) - ccsd_energy
logger.info(cc, 'CCSD energy T3[2] correction : %16.12e', delta_ccsd_energy)
return delta_ccsd_energy, pt1, pt2, Wmcik, Wacek
