#!/usr/bin/env python
# Copyright 2014-2018 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>
#
'''
Restricted coupled pertubed Hartree-Fock solver
'''
import numpy
from pyscf import lib
from pyscf.lib import logger
[docs]
def solve(fvind, mo_energy, mo_occ, h1, s1=None,
max_cycle=20, tol=1e-9, hermi=False, verbose=logger.WARN):
'''
Args:
fvind : function
Given density matrix, compute (ij|kl)D_{lk}*2 - (ij|kl)D_{jk}
Kwargs:
hermi : boolean
Whether the matrix defined by fvind is Hermitian or not.
'''
if s1 is None:
return solve_nos1(fvind, mo_energy, mo_occ, h1,
max_cycle, tol, hermi, verbose)
else:
return solve_withs1(fvind, mo_energy, mo_occ, h1, s1,
max_cycle, tol, hermi, verbose)
kernel = solve
# h1 shape is (:,nvir,nocc)
[docs]
def solve_nos1(fvind, mo_energy, mo_occ, h1,
max_cycle=20, tol=1e-9, hermi=False, verbose=logger.WARN):
'''For field independent basis. First order overlap matrix is zero'''
log = logger.new_logger(verbose=verbose)
t0 = (logger.process_clock(), logger.perf_counter())
e_a = mo_energy[mo_occ==0]
e_i = mo_energy[mo_occ>0]
e_ai = 1 / lib.direct_sum('a-i->ai', e_a, e_i)
mo1base = h1 * -e_ai
def vind_vo(mo1):
v = fvind(mo1.reshape(h1.shape)).reshape(h1.shape)
v *= e_ai
return v.ravel()
mo1 = lib.krylov(vind_vo, mo1base.ravel(),
tol=tol, max_cycle=max_cycle, hermi=hermi, verbose=log)
log.timer('krylov solver in CPHF', *t0)
return mo1.reshape(h1.shape), None
# h1 shape is (:,nocc+nvir,nocc)
[docs]
def solve_withs1(fvind, mo_energy, mo_occ, h1, s1,
max_cycle=20, tol=1e-9, hermi=False, verbose=logger.WARN):
'''For field dependent basis. First order overlap matrix is non-zero.
The first order orbitals are set to
C^1_{ij} = -1/2 S1
e1 = h1 - s1*e0 + (e0_j-e0_i)*c1 + vhf[c1]
Kwargs:
hermi : boolean
Whether the matrix defined by fvind is Hermitian or not.
Returns:
First order orbital coefficients (in MO basis) and first order orbital
energy matrix
'''
log = logger.new_logger(verbose=verbose)
t0 = (logger.process_clock(), logger.perf_counter())
occidx = mo_occ > 0
viridx = mo_occ == 0
e_a = mo_energy[viridx]
e_i = mo_energy[occidx]
e_ai = 1 / lib.direct_sum('a-i->ai', e_a, e_i)
nvir, nocc = e_ai.shape
nmo = nocc + nvir
s1 = s1.reshape(-1,nmo,nocc)
hs = mo1base = h1.reshape(-1,nmo,nocc) - s1*e_i
mo_e1 = hs[:,occidx,:].copy()
mo1base[:,viridx] *= -e_ai
mo1base[:,occidx] = -s1[:,occidx] * .5
def vind_vo(mo1):
v = fvind(mo1.reshape(h1.shape)).reshape(-1,nmo,nocc)
v[:,viridx,:] *= e_ai
v[:,occidx,:] = 0
return v.ravel()
mo1 = lib.krylov(vind_vo, mo1base.ravel(),
tol=tol, max_cycle=max_cycle, hermi=hermi, verbose=log)
mo1 = mo1.reshape(mo1base.shape)
log.timer('krylov solver in CPHF', *t0)
v1mo = fvind(mo1.reshape(h1.shape)).reshape(-1,nmo,nocc)
mo1[:,viridx] = mo1base[:,viridx] - v1mo[:,viridx]*e_ai
# mo_e1 has the same symmetry as the first order Fock matrix (hermitian or
# anti-hermitian). mo_e1 = v1mo - s1*lib.direct_sum('i+j->ij',e_i,e_i)
mo_e1 += mo1[:,occidx] * lib.direct_sum('i-j->ij', e_i, e_i)
mo_e1 += v1mo[:,occidx,:]
if h1.ndim == 3:
return mo1, mo_e1
else:
return mo1.reshape(h1.shape), mo_e1.reshape(nocc,nocc)
if __name__ == '__main__':
numpy.random.seed(1)
nd = 3
nocc = 5
nmo = 12
nvir = nmo - nocc
a = numpy.random.random((nocc*nvir,nocc*nvir))
a = a + a.T
def fvind(x):
v = numpy.dot(a,x[:,nocc:].reshape(-1,nocc*nvir).T)
v1 = numpy.zeros((nd,nmo,nocc))
v1[:,nocc:] = v.T.reshape(nd,nvir,nocc)
return v1
mo_energy = numpy.sort(numpy.random.random(nmo)) * 10
mo_occ = numpy.zeros(nmo)
mo_occ[:nocc] = 2
e_i = mo_energy[mo_occ>0]
e_a = mo_energy[mo_occ==0]
e_ai = 1 / lib.direct_sum('a-i->ai', e_a, e_i)
h1 = numpy.random.random((nd,nmo,nocc))
h1[:,:nocc,:nocc] = h1[:,:nocc,:nocc] + h1[:,:nocc,:nocc].transpose(0,2,1)
s1 = numpy.random.random((nd,nmo,nocc))
s1[:,:nocc,:nocc] = s1[:,:nocc,:nocc] + s1[:,:nocc,:nocc].transpose(0,2,1)
x = solve(fvind, mo_energy, mo_occ, h1, s1, max_cycle=30)[0]
print(numpy.linalg.norm(x)-6.272581531366389)
hs = h1.reshape(-1,nmo,nocc) - s1.reshape(-1,nmo,nocc)*e_i
print(abs(hs[:,nocc:] + fvind(x)[:,nocc:]+x[:,nocc:]/e_ai).sum())
################
xref = solve(fvind, mo_energy, mo_occ, h1, s1*0, max_cycle=30)[0][:,mo_occ==0]
def fvind(x):
return numpy.dot(a,x.reshape(nd,nocc*nvir).T).T.reshape(nd,nvir,nocc)
h1 = h1[:,nocc:]
x0 = numpy.linalg.solve(numpy.diag(1/e_ai.ravel())+a, -h1.reshape(nd,-1).T).T.reshape(nd,nvir,nocc)
x1 = solve(fvind, mo_energy, mo_occ, h1, max_cycle=30)[0]
print(abs(x0-x1).sum())
print(abs(xref-x1).sum())
print(abs(h1 + fvind(x1)+x1/e_ai).sum())