#!/usr/bin/env python
# Copyright 2021-2022 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>
#
'''
TDA and TDHF for no-pair DKS Hamiltonian
'''
from functools import reduce
import numpy
from pyscf import lib
from pyscf import dft
from pyscf import ao2mo
from pyscf.lib import logger
from pyscf.tdscf import rhf
from pyscf.data import nist
from pyscf import __config__
OUTPUT_THRESHOLD = getattr(__config__, 'tdscf_uhf_get_nto_threshold', 0.3)
REAL_EIG_THRESHOLD = getattr(__config__, 'tdscf_uhf_TDDFT_pick_eig_threshold', 1e-4)
[docs]
def gen_tda_operation(mf, fock_ao=None):
'''A x
'''
mo_coeff = mf.mo_coeff
mo_energy = mf.mo_energy
mo_occ = mf.mo_occ
nao, nmo = mo_coeff.shape
# Remove all negative states
n2c = nmo // 2
occidx = n2c + numpy.where(mo_occ[n2c:] == 1)[0]
viridx = n2c + numpy.where(mo_occ[n2c:] == 0)[0]
nocc = len(occidx)
nvir = len(viridx)
orbv = mo_coeff[:,viridx]
orbo = mo_coeff[:,occidx]
if fock_ao is None:
#dm0 = mf.make_rdm1(mo_coeff, mo_occ)
#fock_ao = mf.get_hcore() + mf.get_veff(mol, dm0)
foo = numpy.diag(mo_energy[occidx])
fvv = numpy.diag(mo_energy[viridx])
else:
fock = reduce(numpy.dot, (mo_coeff.conj().T, fock_ao, mo_coeff))
foo = fock[occidx[:,None],occidx]
fvv = fock[viridx[:,None],viridx]
hdiag = (fvv.diagonal() - foo.diagonal()[:,None]).ravel()
mo_coeff = numpy.asarray(numpy.hstack((orbo,orbv)), order='F')
vresp = mf.gen_response(hermi=0)
def vind(zs):
zs = numpy.asarray(zs).reshape(-1,nocc,nvir)
dmov = lib.einsum('xov,qv,po->xpq', zs, orbv.conj(), orbo)
v1ao = vresp(dmov)
v1ov = lib.einsum('xpq,po,qv->xov', v1ao, orbo.conj(), orbv)
v1ov += lib.einsum('xqs,sp->xqp', zs, fvv)
v1ov -= lib.einsum('xpr,sp->xsr', zs, foo)
return v1ov.reshape(v1ov.shape[0], -1)
return vind, hdiag
gen_tda_hop = gen_tda_operation
[docs]
def get_ab(mf, mo_energy=None, mo_coeff=None, mo_occ=None):
r'''A and B matrices for TDDFT response function.
A[i,a,j,b] = \delta_{ab}\delta_{ij}(E_a - E_i) + (ia||bj)
B[i,a,j,b] = (ia||jb)
'''
if mo_energy is None: mo_energy = mf.mo_energy
if mo_coeff is None: mo_coeff = mf.mo_coeff
if mo_occ is None: mo_occ = mf.mo_occ
mol = mf.mol
nao, nmo = mo_coeff.shape
n2c = nmo // 2
occidx = n2c + numpy.where(mo_occ[n2c:] == 1)[0]
viridx = n2c + numpy.where(mo_occ[n2c:] == 0)[0]
orbv = mo_coeff[:,viridx]
orbo = mo_coeff[:,occidx]
nvir = orbv.shape[1]
nocc = orbo.shape[1]
nmo = nocc + nvir
mo = numpy.hstack((orbo, orbv))
c1 = .5 / lib.param.LIGHT_SPEED
moL = numpy.asarray(mo[:n2c], order='F')
moS = numpy.asarray(mo[n2c:], order='F') * c1
orboL = moL[:,:nocc]
orboS = moS[:,:nocc]
e_ia = lib.direct_sum('a-i->ia', mo_energy[viridx], mo_energy[occidx])
a = numpy.diag(e_ia.ravel()).reshape(nocc,nvir,nocc,nvir)
b = numpy.zeros_like(a)
def add_hf_(a, b, hyb=1):
eri_mo = ao2mo.kernel(mol, [orboL, moL, moL, moL], intor='int2e_spinor')
eri_mo+= ao2mo.kernel(mol, [orboS, moS, moS, moS], intor='int2e_spsp1spsp2_spinor')
eri_mo+= ao2mo.kernel(mol, [orboS, moS, moL, moL], intor='int2e_spsp1_spinor')
eri_mo+= ao2mo.kernel(mol, [moS, moS, orboL, moL], intor='int2e_spsp1_spinor').T
eri_mo = eri_mo.reshape(nocc,nmo,nmo,nmo)
a = a + numpy.einsum('iabj->iajb', eri_mo[:nocc,nocc:,nocc:,:nocc])
a = a - numpy.einsum('ijba->iajb', eri_mo[:nocc,:nocc,nocc:,nocc:]) * hyb
b = b + numpy.einsum('iajb->iajb', eri_mo[:nocc,nocc:,:nocc,nocc:])
b = b - numpy.einsum('jaib->iajb', eri_mo[:nocc,nocc:,:nocc,nocc:]) * hyb
return a, b
if isinstance(mf, dft.KohnShamDFT):
from pyscf.dft import xc_deriv
ni = mf._numint
ni.libxc.test_deriv_order(mf.xc, 2, raise_error=True)
if mf.nlc or ni.libxc.is_nlc(mf.xc):
raise NotImplementedError('DKS-TDDFT for NLC functionals')
omega, alpha, hyb = ni.rsh_and_hybrid_coeff(mf.xc, mol.spin)
a, b = add_hf_(a, b, hyb)
xctype = ni._xc_type(mf.xc)
dm0 = mf.make_rdm1(mo_coeff, mo_occ)
mem_now = lib.current_memory()[0]
max_memory = max(2000, mf.max_memory*.8-mem_now)
def get_mo_value(ao):
aoLa, aoLb, aoSa, aoSb = ao
if aoLa.ndim == 2:
moLa = lib.einsum('rp,pi->ri', aoLa, moL)
moLb = lib.einsum('rp,pi->ri', aoLb, moL)
moSa = lib.einsum('rp,pi->ri', aoSa, moS)
moSb = lib.einsum('rp,pi->ri', aoSb, moS)
return (moLa[:,:nocc], moLa[:,nocc:], moLb[:,:nocc], moLb[:,nocc:],
moSa[:,:nocc], moSa[:,nocc:], moSb[:,:nocc], moSb[:,nocc:])
else:
moLa = lib.einsum('xrp,pi->xri', aoLa, moL)
moLb = lib.einsum('xrp,pi->xri', aoLb, moL)
moSa = lib.einsum('xrp,pi->xri', aoSa, moS)
moSb = lib.einsum('xrp,pi->xri', aoSb, moS)
return (moLa[:,:,:nocc], moLa[:,:,nocc:], moLb[:,:,:nocc], moLb[:,:,nocc:],
moSa[:,:,:nocc], moSa[:,:,nocc:], moSb[:,:,:nocc], moSb[:,:,nocc:])
def ud2tm(aa, ab, ba, bb):
return numpy.stack([aa + bb, # rho
ba + ab, # mx
(ba - ab) * 1j, # my
aa - bb]) # mz
def addLS(rhoL, rhoS):
rhoS[1:4] *= -1 # beta * Sigma
return rhoL + rhoS
if xctype == 'LDA':
ao_deriv = 0
for ao, mask, weight, coords \
in ni.block_loop(mol, mf.grids, nao, ao_deriv, max_memory,
with_s=True):
if ni.collinear[0] == 'm':
rho = ni.eval_rho(mol, ao, dm0, mask, xctype, hermi=1, with_lapl=False)
eval_xc = ni.mcfun_eval_xc_adapter(mf.xc)
fxc = eval_xc(mf.xc, rho, deriv=2, xctype=xctype)[2]
wfxc = weight * fxc.reshape(4,4,-1)
moLoa, moLva, moLob, moLvb, moSoa, moSva, moSob, moSvb = get_mo_value(ao)
rhoL_ov_aa = numpy.einsum('ri,ra->ria', moLoa.conj(), moLva)
rhoL_ov_ab = numpy.einsum('ri,ra->ria', moLoa.conj(), moLvb)
rhoL_ov_ba = numpy.einsum('ri,ra->ria', moLob.conj(), moLva)
rhoL_ov_bb = numpy.einsum('ri,ra->ria', moLob.conj(), moLvb)
rhoS_ov_aa = numpy.einsum('ri,ra->ria', moSoa.conj(), moSva)
rhoS_ov_ab = numpy.einsum('ri,ra->ria', moSoa.conj(), moSvb)
rhoS_ov_ba = numpy.einsum('ri,ra->ria', moSob.conj(), moSva)
rhoS_ov_bb = numpy.einsum('ri,ra->ria', moSob.conj(), moSvb)
rhoL_ov = ud2tm(rhoL_ov_aa, rhoL_ov_ab, rhoL_ov_ba, rhoL_ov_bb)
rhoS_ov = ud2tm(rhoS_ov_aa, rhoS_ov_ab, rhoS_ov_ba, rhoS_ov_bb)
rho_ov = addLS(rhoL_ov, rhoS_ov)
rho_vo = rho_ov.conj()
w_ov = numpy.einsum('tsr,tria->sria', wfxc, rho_ov)
a += lib.einsum('sria,srjb->iajb', w_ov, rho_vo)
b += lib.einsum('sria,srjb->iajb', w_ov, rho_ov)
elif ni.collinear[0] == 'c':
rho = ni.eval_rho(mol, ao, dm0, mask, xctype, hermi=1, with_lapl=False)
fxc = ni.eval_xc_eff(mf.xc, rho, deriv=2)[2]
wv_a, wv_b = weight * fxc.reshape(2,2,-1)
moLoa, moLva, moLob, moLvb, moSoa, moSva, moSob, moSvb = get_mo_value(ao)
rhoL_ov_a = numpy.einsum('ri,ra->ria', moLoa.conj(), moLva)
rhoL_ov_b = numpy.einsum('ri,ra->ria', moLob.conj(), moLvb)
rhoS_ov_a = numpy.einsum('ri,ra->ria', moSoa.conj(), moSva)
rhoS_ov_b = numpy.einsum('ri,ra->ria', moSob.conj(), moSvb)
rhoL_vo_a = rhoL_ov_a.conj()
rhoL_vo_b = rhoL_ov_b.conj()
rhoS_vo_a = rhoS_ov_a.conj()
rhoS_vo_b = rhoS_ov_b.conj()
w_ov = wv_a[:,:,None,None] * rhoL_ov_a
w_ov += wv_b[:,:,None,None] * rhoL_ov_b
w_ov += wv_b[:,:,None,None] * rhoS_ov_a # for beta*Sigma
w_ov += wv_a[:,:,None,None] * rhoS_ov_b
wa_ov, wb_ov = w_ov
a += lib.einsum('ria,rjb->iajb', wa_ov, rhoL_vo_a)
a += lib.einsum('ria,rjb->iajb', wb_ov, rhoL_vo_b)
a += lib.einsum('ria,rjb->iajb', wb_ov, rhoS_vo_a)
a += lib.einsum('ria,rjb->iajb', wa_ov, rhoS_vo_b)
b += lib.einsum('ria,rjb->iajb', wa_ov, rhoL_ov_a)
b += lib.einsum('ria,rjb->iajb', wb_ov, rhoL_ov_b)
b += lib.einsum('ria,rjb->iajb', wb_ov, rhoS_ov_a)
b += lib.einsum('ria,rjb->iajb', wa_ov, rhoS_ov_b)
else:
raise NotImplementedError(ni.collinear)
elif xctype == 'GGA':
ao_deriv = 1
for ao, mask, weight, coords \
in ni.block_loop(mol, mf.grids, nao, ao_deriv, max_memory,
with_s=True):
if ni.collinear[0] == 'm':
rho = ni.eval_rho(mol, ao, dm0, mask, xctype, hermi=1, with_lapl=False)
eval_xc = ni.mcfun_eval_xc_adapter(mf.xc)
fxc = eval_xc(mf.xc, rho, deriv=2, xctype=xctype)[2]
wfxc = weight * fxc
moLoa, moLva, moLob, moLvb, moSoa, moSva, moSob, moSvb = get_mo_value(ao)
rhoL_ov_aa = numpy.einsum('ri,xra->xria', moLoa[0].conj(), moLva)
rhoL_ov_ab = numpy.einsum('ri,xra->xria', moLoa[0].conj(), moLvb)
rhoL_ov_ba = numpy.einsum('ri,xra->xria', moLob[0].conj(), moLva)
rhoL_ov_bb = numpy.einsum('ri,xra->xria', moLob[0].conj(), moLvb)
rhoS_ov_aa = numpy.einsum('ri,xra->xria', moSoa[0].conj(), moSva)
rhoS_ov_ab = numpy.einsum('ri,xra->xria', moSoa[0].conj(), moSvb)
rhoS_ov_ba = numpy.einsum('ri,xra->xria', moSob[0].conj(), moSva)
rhoS_ov_bb = numpy.einsum('ri,xra->xria', moSob[0].conj(), moSvb)
rhoL_ov_aa[1:4] += numpy.einsum('xri,ra->xria', moLoa[1:4].conj(), moLva[0])
rhoL_ov_ab[1:4] += numpy.einsum('xri,ra->xria', moLoa[1:4].conj(), moLvb[0])
rhoL_ov_ba[1:4] += numpy.einsum('xri,ra->xria', moLob[1:4].conj(), moLva[0])
rhoL_ov_bb[1:4] += numpy.einsum('xri,ra->xria', moLob[1:4].conj(), moLvb[0])
rhoS_ov_aa[1:4] += numpy.einsum('xri,ra->xria', moSoa[1:4].conj(), moSva[0])
rhoS_ov_ab[1:4] += numpy.einsum('xri,ra->xria', moSoa[1:4].conj(), moSvb[0])
rhoS_ov_ba[1:4] += numpy.einsum('xri,ra->xria', moSob[1:4].conj(), moSva[0])
rhoS_ov_bb[1:4] += numpy.einsum('xri,ra->xria', moSob[1:4].conj(), moSvb[0])
rhoL_ov = ud2tm(rhoL_ov_aa, rhoL_ov_ab, rhoL_ov_ba, rhoL_ov_bb)
rhoS_ov = ud2tm(rhoS_ov_aa, rhoS_ov_ab, rhoS_ov_ba, rhoS_ov_bb)
rho_ov = addLS(rhoL_ov, rhoS_ov)
rho_vo = rho_ov.conj()
w_ov = numpy.einsum('txsyr,txria->syria', wfxc, rho_ov)
a += lib.einsum('syria,syrjb->iajb', w_ov, rho_vo)
b += lib.einsum('syria,syrjb->iajb', w_ov, rho_ov)
elif ni.collinear[0] == 'c':
rho = ni.eval_rho(mol, ao, dm0, mask, xctype, hermi=1, with_lapl=False)
fxc = ni.eval_xc_eff(mf.xc, rho, deriv=2)[2]
fxc = xc_deriv.ud2ts(fxc)
wfxc = weight * fxc
moLoa, moLva, moLob, moLvb, moSoa, moSva, moSob, moSvb = get_mo_value(ao)
rhoL_ov_a = numpy.einsum('xri,ra->xria', moLoa.conj(), moLva[0])
rhoL_ov_b = numpy.einsum('xri,ra->xria', moLob.conj(), moLvb[0])
rhoL_ov_a[1:4] += numpy.einsum('ri,xra->xria', moLoa[0].conj(), moLva[1:4])
rhoL_ov_b[1:4] += numpy.einsum('ri,xra->xria', moLob[0].conj(), moLvb[1:4])
rhoS_ov_a = numpy.einsum('xri,ra->xria', moSoa.conj(), moSva[0])
rhoS_ov_b = numpy.einsum('xri,ra->xria', moSob.conj(), moSvb[0])
rhoS_ov_a[1:4] += numpy.einsum('ri,xra->xria', moSoa[0].conj(), moSva[1:4])
rhoS_ov_b[1:4] += numpy.einsum('ri,xra->xria', moSob[0].conj(), moSvb[1:4])
rhoL_ov = numpy.stack((rhoL_ov_a+rhoL_ov_b, rhoL_ov_a-rhoL_ov_b))
rhoS_ov = numpy.stack((rhoS_ov_a+rhoS_ov_b, rhoS_ov_a-rhoS_ov_b))
rhoS_ov[1] *= -1
rho_ov = rhoL_ov + rhoS_ov
rho_vo = rho_ov.conj()
w_ov = numpy.einsum('txsyr,txria->syria', wfxc, rho_ov)
a += lib.einsum('syria,syrjb->iajb', w_ov, rho_vo)
b += lib.einsum('syria,syrjb->iajb', w_ov, rho_ov)
else:
raise NotImplementedError(ni.collinear)
elif xctype == 'HF':
pass
elif xctype == 'NLC':
raise NotImplementedError('NLC')
elif xctype == 'MGGA':
ao_deriv = 1
for ao, mask, weight, coords \
in ni.block_loop(mol, mf.grids, nao, ao_deriv, max_memory,
with_s=True):
if ni.collinear[0] == 'm':
rho = ni.eval_rho(mol, ao, dm0, mask, xctype, hermi=1, with_lapl=False)
eval_xc = ni.mcfun_eval_xc_adapter(mf.xc)
fxc = eval_xc(mf.xc, rho, deriv=2, xctype=xctype)[2]
wfxc = weight * fxc
moLoa, moLva, moLob, moLvb, moSoa, moSva, moSob, moSvb = get_mo_value(ao)
rhoL_ov_aa = numpy.einsum('ri,xra->xria', moLoa[0].conj(), moLva)
rhoL_ov_ab = numpy.einsum('ri,xra->xria', moLoa[0].conj(), moLvb)
rhoL_ov_ba = numpy.einsum('ri,xra->xria', moLob[0].conj(), moLva)
rhoL_ov_bb = numpy.einsum('ri,xra->xria', moLob[0].conj(), moLvb)
rhoS_ov_aa = numpy.einsum('ri,xra->xria', moSoa[0].conj(), moSva)
rhoS_ov_ab = numpy.einsum('ri,xra->xria', moSoa[0].conj(), moSvb)
rhoS_ov_ba = numpy.einsum('ri,xra->xria', moSob[0].conj(), moSva)
rhoS_ov_bb = numpy.einsum('ri,xra->xria', moSob[0].conj(), moSvb)
rhoL_ov_aa[1:4] += numpy.einsum('xri,ra->xria', moLoa[1:4].conj(), moLva[0])
rhoL_ov_ab[1:4] += numpy.einsum('xri,ra->xria', moLoa[1:4].conj(), moLvb[0])
rhoL_ov_ba[1:4] += numpy.einsum('xri,ra->xria', moLob[1:4].conj(), moLva[0])
rhoL_ov_bb[1:4] += numpy.einsum('xri,ra->xria', moLob[1:4].conj(), moLvb[0])
rhoS_ov_aa[1:4] += numpy.einsum('xri,ra->xria', moSoa[1:4].conj(), moSva[0])
rhoS_ov_ab[1:4] += numpy.einsum('xri,ra->xria', moSoa[1:4].conj(), moSvb[0])
rhoS_ov_ba[1:4] += numpy.einsum('xri,ra->xria', moSob[1:4].conj(), moSva[0])
rhoS_ov_bb[1:4] += numpy.einsum('xri,ra->xria', moSob[1:4].conj(), moSvb[0])
tauL_ov_aa = numpy.einsum('xri,xra->ria', moLoa[1:4].conj(), moLva[1:4]) * .5
tauL_ov_ab = numpy.einsum('xri,xra->ria', moLoa[1:4].conj(), moLvb[1:4]) * .5
tauL_ov_ba = numpy.einsum('xri,xra->ria', moLob[1:4].conj(), moLva[1:4]) * .5
tauL_ov_bb = numpy.einsum('xri,xra->ria', moLob[1:4].conj(), moLvb[1:4]) * .5
tauS_ov_aa = numpy.einsum('xri,xra->ria', moSoa[1:4].conj(), moSva[1:4]) * .5
tauS_ov_ab = numpy.einsum('xri,xra->ria', moSoa[1:4].conj(), moSvb[1:4]) * .5
tauS_ov_ba = numpy.einsum('xri,xra->ria', moSob[1:4].conj(), moSva[1:4]) * .5
tauS_ov_bb = numpy.einsum('xri,xra->ria', moSob[1:4].conj(), moSvb[1:4]) * .5
rhoL_ov_aa = numpy.vstack([rhoL_ov_aa, tauL_ov_aa[numpy.newaxis]])
rhoL_ov_ab = numpy.vstack([rhoL_ov_ab, tauL_ov_ab[numpy.newaxis]])
rhoL_ov_ba = numpy.vstack([rhoL_ov_ba, tauL_ov_ba[numpy.newaxis]])
rhoL_ov_bb = numpy.vstack([rhoL_ov_bb, tauL_ov_bb[numpy.newaxis]])
rhoS_ov_aa = numpy.vstack([rhoS_ov_aa, tauS_ov_aa[numpy.newaxis]])
rhoS_ov_ab = numpy.vstack([rhoS_ov_ab, tauS_ov_ab[numpy.newaxis]])
rhoS_ov_ba = numpy.vstack([rhoS_ov_ba, tauS_ov_ba[numpy.newaxis]])
rhoS_ov_bb = numpy.vstack([rhoS_ov_bb, tauS_ov_bb[numpy.newaxis]])
rhoL_ov = ud2tm(rhoL_ov_aa, rhoL_ov_ab, rhoL_ov_ba, rhoL_ov_bb)
rhoS_ov = ud2tm(rhoS_ov_aa, rhoS_ov_ab, rhoS_ov_ba, rhoS_ov_bb)
rho_ov = addLS(rhoL_ov, rhoS_ov)
rho_vo = rho_ov.conj()
w_ov = numpy.einsum('txsyr,txria->syria', wfxc, rho_ov)
a += lib.einsum('syria,syrjb->iajb', w_ov, rho_vo)
b += lib.einsum('syria,syrjb->iajb', w_ov, rho_ov)
elif ni.collinear[0] == 'c':
rho = ni.eval_rho(mol, ao, dm0, mask, xctype, hermi=1, with_lapl=False)
fxc = ni.eval_xc_eff(mf.xc, rho, deriv=2)[2]
fxc = xc_deriv.ud2ts(fxc)
wfxc = weight * fxc
moLoa, moLva, moLob, moLvb, moSoa, moSva, moSob, moSvb = get_mo_value(ao)
rhoL_ov_a = numpy.einsum('xri,ra->xria', moLoa.conj(), moLva[0])
rhoL_ov_b = numpy.einsum('xri,ra->xria', moLob.conj(), moLvb[0])
rhoS_ov_a = numpy.einsum('xri,ra->xria', moSoa.conj(), moSva[0])
rhoS_ov_b = numpy.einsum('xri,ra->xria', moSob.conj(), moSvb[0])
rhoL_ov_a[1:4] += numpy.einsum('ri,xra->xria', moLoa[0].conj(), moLva[1:4])
rhoL_ov_b[1:4] += numpy.einsum('ri,xra->xria', moLob[0].conj(), moLvb[1:4])
rhoS_ov_a[1:4] += numpy.einsum('ri,xra->xria', moSoa[0].conj(), moSva[1:4])
rhoS_ov_b[1:4] += numpy.einsum('ri,xra->xria', moSob[0].conj(), moSvb[1:4])
tauL_ov_a = numpy.einsum('xri,xra->ria', moLoa[1:4].conj(), moLva[1:4]) * .5
tauL_ov_b = numpy.einsum('xri,xra->ria', moLob[1:4].conj(), moLvb[1:4]) * .5
tauS_ov_a = numpy.einsum('xri,xra->ria', moSoa[1:4].conj(), moSva[1:4]) * .5
tauS_ov_b = numpy.einsum('xri,xra->ria', moSob[1:4].conj(), moSvb[1:4]) * .5
rhoL_ov_a = numpy.vstack([rhoL_ov_a, tauL_ov_a[numpy.newaxis]])
rhoL_ov_b = numpy.vstack([rhoL_ov_b, tauL_ov_b[numpy.newaxis]])
rhoS_ov_a = numpy.vstack([rhoS_ov_a, tauS_ov_a[numpy.newaxis]])
rhoS_ov_b = numpy.vstack([rhoS_ov_b, tauS_ov_b[numpy.newaxis]])
rhoL_ov = numpy.stack((rhoL_ov_a+rhoL_ov_b, rhoL_ov_a-rhoL_ov_b))
rhoS_ov = numpy.stack((rhoS_ov_a+rhoS_ov_b, rhoS_ov_a-rhoS_ov_b))
rhoS_ov[1] *= -1
rho_ov = rhoL_ov + rhoS_ov
rho_vo = rho_ov.conj()
w_ov = numpy.einsum('txsyr,txria->syria', wfxc, rho_ov)
a += lib.einsum('syria,syrjb->iajb', w_ov, rho_vo)
b += lib.einsum('syria,syrjb->iajb', w_ov, rho_ov)
else:
raise NotImplementedError(ni.collinear)
else:
a, b = add_hf_(a, b)
return a, b
[docs]
def get_nto(tdobj, state=1, threshold=OUTPUT_THRESHOLD, verbose=None):
raise NotImplementedError('get_nto')
[docs]
def analyze(tdobj, verbose=None):
raise NotImplementedError('analyze')
def _contract_multipole(tdobj, ints, hermi=True, xy=None):
raise NotImplementedError
[docs]
class TDBase(rhf.TDBase):
[docs]
@lib.with_doc(get_ab.__doc__)
def get_ab(self, mf=None):
if mf is None: mf = self._scf
return get_ab(mf)
analyze = analyze
get_nto = get_nto
_contract_multipole = _contract_multipole # needed by transition dipoles
[docs]
def nuc_grad_method(self):
raise NotImplementedError
[docs]
@lib.with_doc(rhf.TDA.__doc__)
class TDA(TDBase):
[docs]
def gen_vind(self, mf=None):
'''Generate function to compute Ax'''
if mf is None:
mf = self._scf
return gen_tda_hop(mf)
[docs]
def init_guess(self, mf, nstates=None, wfnsym=None):
if nstates is None: nstates = self.nstates
mo_energy = mf.mo_energy
mo_occ = mf.mo_occ
# Remove all negative states
n2c = mf.mo_occ.size // 2
occidx = n2c + numpy.where(mo_occ[n2c:] == 1)[0]
viridx = n2c + numpy.where(mo_occ[n2c:] == 0)[0]
e_ia = mo_energy[viridx] - mo_energy[occidx,None]
nov = e_ia.size
nstates = min(nstates, nov)
e_ia = e_ia.ravel()
e_threshold = numpy.sort(e_ia)[nstates-1]
e_threshold += self.deg_eia_thresh
idx = numpy.where(e_ia <= e_threshold)[0]
x0 = numpy.zeros((idx.size, nov))
for i, j in enumerate(idx):
x0[i, j] = 1 # Koopmans' excitations
return x0
[docs]
def kernel(self, x0=None, nstates=None):
'''TDA diagonalization solver
'''
cpu0 = (logger.process_clock(), logger.perf_counter())
self.check_sanity()
self.dump_flags()
if nstates is None:
nstates = self.nstates
else:
self.nstates = nstates
log = logger.Logger(self.stdout, self.verbose)
vind, hdiag = self.gen_vind(self._scf)
precond = self.get_precond(hdiag)
def pickeig(w, v, nroots, envs):
idx = numpy.where(w > self.positive_eig_threshold)[0]
return w[idx], v[:,idx], idx
if x0 is None:
x0 = self.init_guess(self._scf, self.nstates)
# FIXME: Is it correct to call davidson1 for complex integrals?
self.converged, self.e, x1 = \
lib.davidson1(vind, x0, precond,
tol=self.conv_tol,
nroots=nstates, lindep=self.lindep,
max_cycle=self.max_cycle,
max_space=self.max_space, pick=pickeig,
verbose=log)
nocc = (self._scf.mo_occ>0).sum()
nmo = self._scf.mo_occ.size
n2c = nmo // 2
nvir = n2c - nocc
self.xy = [(xi.reshape(nocc,nvir), 0) for xi in x1]
if self.chkfile:
lib.chkfile.save(self.chkfile, 'tddft/e', self.e)
lib.chkfile.save(self.chkfile, 'tddft/xy', self.xy)
log.timer('TDA', *cpu0)
self._finalize()
return self.e, self.xy
[docs]
def gen_tdhf_operation(mf, fock_ao=None):
'''Generate function to compute
[ A B ][X]
[-B* -A*][Y]
'''
mo_coeff = mf.mo_coeff
mo_energy = mf.mo_energy
mo_occ = mf.mo_occ
nao, nmo = mo_coeff.shape
n2c = nmo // 2
occidx = n2c + numpy.where(mo_occ[n2c:] == 1)[0]
viridx = n2c + numpy.where(mo_occ[n2c:] == 0)[0]
nocc = len(occidx)
nvir = len(viridx)
orbv = mo_coeff[:,viridx]
orbo = mo_coeff[:,occidx]
foo = numpy.diag(mo_energy[occidx])
fvv = numpy.diag(mo_energy[viridx])
hdiag = fvv.diagonal() - foo.diagonal()[:,None]
hdiag = numpy.hstack((hdiag.ravel(), -hdiag.ravel())).real
mo_coeff = numpy.asarray(numpy.hstack((orbo,orbv)), order='F')
vresp = mf.gen_response(hermi=0)
def vind(xys):
xys = numpy.asarray(xys).reshape(-1,2,nocc,nvir)
xs, ys = xys.transpose(1,0,2,3)
# dms = AX + BY
dms = lib.einsum('xov,qv,po->xpq', xs, orbv.conj(), orbo)
dms += lib.einsum('xov,pv,qo->xpq', ys, orbv, orbo.conj())
v1ao = vresp(dms)
v1ov = lib.einsum('xpq,po,qv->xov', v1ao, orbo.conj(), orbv)
v1vo = lib.einsum('xpq,qo,pv->xov', v1ao, orbo, orbv.conj())
v1ov += lib.einsum('xqs,sp->xqp', xs, fvv) # AX
v1ov -= lib.einsum('xpr,sp->xsr', xs, foo) # AX
v1vo += lib.einsum('xqs,sp->xqp', ys, fvv.conj()) # (A*)Y
v1vo -= lib.einsum('xpr,sp->xsr', ys, foo.conj()) # (A*)Y
# (AX, (-A*)Y)
nz = xys.shape[0]
hx = numpy.hstack((v1ov.reshape(nz,-1), -v1vo.reshape(nz,-1)))
return hx
return vind, hdiag
[docs]
class TDHF(TDBase):
[docs]
@lib.with_doc(gen_tdhf_operation.__doc__)
def gen_vind(self, mf=None):
if mf is None:
mf = self._scf
return gen_tdhf_operation(mf)
[docs]
def init_guess(self, mf, nstates=None, wfnsym=None):
x0 = TDA.init_guess(self, mf, nstates, wfnsym)
y0 = numpy.zeros_like(x0)
return numpy.asarray(numpy.block([[x0, y0], [y0, x0.conj()]]))
[docs]
def kernel(self, x0=None, nstates=None):
'''TDHF diagonalization with non-Hermitian eigenvalue solver
'''
cpu0 = (logger.process_clock(), logger.perf_counter())
self.check_sanity()
self.dump_flags()
if nstates is None:
nstates = self.nstates
else:
self.nstates = nstates
log = logger.Logger(self.stdout, self.verbose)
vind, hdiag = self.gen_vind(self._scf)
precond = self.get_precond(hdiag)
def pickeig(w, v, nroots, envs):
realidx = numpy.where((abs(w.imag) < REAL_EIG_THRESHOLD) &
(w.real > self.positive_eig_threshold))[0]
# FIXME: Should the amplitudes be real?
return lib.linalg_helper._eigs_cmplx2real(w, v, realidx,
real_eigenvectors=False)
if x0 is None:
x0 = self.init_guess(self._scf, self.nstates)
self.converged, w, x1 = \
lib.davidson_nosym1(vind, x0, precond,
tol=self.conv_tol,
nroots=nstates, lindep=self.lindep,
max_cycle=self.max_cycle,
max_space=self.max_space, pick=pickeig,
verbose=log)
nocc = (self._scf.mo_occ>0).sum()
nmo = self._scf.mo_occ.size
n2c = nmo // 2
nvir = n2c - nocc
self.e = w
def norm_xy(z):
x, y = z.reshape(2,nocc,nvir)
norm = lib.norm(x)**2 - lib.norm(y)**2
norm = numpy.sqrt(1./norm)
return x*norm, y*norm
self.xy = [norm_xy(z) for z in x1]
if self.chkfile:
lib.chkfile.save(self.chkfile, 'tddft/e', self.e)
lib.chkfile.save(self.chkfile, 'tddft/xy', self.xy)
log.timer('TDDFT', *cpu0)
self._finalize()
return self.e, self.xy
from pyscf import scf
scf.dhf.DHF.TDA = scf.dhf.RDHF.TDA = lib.class_as_method(TDA)
scf.dhf.DHF.TDHF = scf.dhf.RDHF.TDHF = lib.class_as_method(TDHF)
del (OUTPUT_THRESHOLD)