#!/usr/bin/env python
#
# Author: Qiming Sun <osirpt.sun@gmail.com>
#
'''
A, B matrices of TDDFT method.
'''
import numpy
from pyscf import gto, scf, dft, tddft
mol = gto.Mole()
mol.atom = [
['H' , (0. , 0. , .917)],
['F' , (0. , 0. , 0.)], ]
mol.basis = '6311g*'
mol.build()
#
# RHF/RKS-TDDFT
#
def diagonalize(a, b, nroots=5):
nocc, nvir = a.shape[:2]
a = a.reshape(nocc*nvir,nocc*nvir)
b = b.reshape(nocc*nvir,nocc*nvir)
e = numpy.linalg.eig(numpy.bmat([[a , b ],
[-b.conj(),-a.conj()]]))[0]
lowest_e = numpy.sort(e[e > 0])[:nroots]
return lowest_e
mf = scf.RHF(mol).run()
a, b = tddft.TDHF(mf).get_ab()
print('Direct diagoanlization:', diagonalize(a, b))
print('Reference:', tddft.TDHF(mf).kernel(nstates=5)[0])
mf = dft.RKS(mol).run(xc='lda,vwn')
a, b = tddft.TDDFT(mf).get_ab()
print('Direct diagoanlization:', diagonalize(a, b))
print('Reference:', tddft.TDDFT(mf).kernel(nstates=5)[0])
mf = dft.RKS(mol).run(xc='b3lyp')
a, b = tddft.TDDFT(mf).get_ab()
print('Direct diagoanlization:', diagonalize(a, b))
print('Reference:', tddft.TDDFT(mf).kernel(nstates=5)[0])
#
# UHF/UKS-TDDFT
#
def diagonalize(a, b, nroots=4):
a_aa, a_ab, a_bb = a
b_aa, b_ab, b_bb = b
nocc_a, nvir_a, nocc_b, nvir_b = a_ab.shape
a_aa = a_aa.reshape((nocc_a*nvir_a,nocc_a*nvir_a))
a_ab = a_ab.reshape((nocc_a*nvir_a,nocc_b*nvir_b))
a_bb = a_bb.reshape((nocc_b*nvir_b,nocc_b*nvir_b))
b_aa = b_aa.reshape((nocc_a*nvir_a,nocc_a*nvir_a))
b_ab = b_ab.reshape((nocc_a*nvir_a,nocc_b*nvir_b))
b_bb = b_bb.reshape((nocc_b*nvir_b,nocc_b*nvir_b))
a = numpy.bmat([[ a_aa , a_ab],
[ a_ab.T, a_bb]])
b = numpy.bmat([[ b_aa , b_ab],
[ b_ab.T, b_bb]])
e = numpy.linalg.eig(numpy.bmat([[a , b ],
[-b.conj(),-a.conj()]]))[0]
lowest_e = numpy.sort(e[e.real > 0].real)[:nroots]
return lowest_e
mol.spin = 2
mf = scf.UHF(mol).run()
a, b = tddft.TDHF(mf).get_ab()
print('Direct diagoanlization:', diagonalize(a, b))
print('Reference:', tddft.TDHF(mf).kernel(nstates=4)[0])
mf = dft.UKS(mol).run(xc='lda,vwn')
a, b = tddft.TDDFT(mf).get_ab()
print('Direct diagoanlization:', diagonalize(a, b))
print('Reference:', tddft.TDDFT(mf).kernel(nstates=4)[0])
mf = dft.UKS(mol).run(xc='b3lyp')
a, b = tddft.TDDFT(mf).get_ab()
print('Direct diagoanlization:', diagonalize(a, b))
print('Reference:', tddft.TDDFT(mf).kernel(nstates=4)[0])
