def test_153_bse_h2b_uks_rpa(self):
""" This example is with discrepancies... """
mol = gto.M(verbose=1,
atom='B 0 0 0; H 0 0.489 1.074; H 0 0.489 -1.074',
basis='cc-pvdz',
spin=3)
gto_mf = scf.UKS(mol)
gto_mf.kernel()
gto_td = tddft.dRPA(gto_mf)
gto_td.nstates = 190
gto_td.kernel()
omegas = np.arange(0.0, 2.0, 0.01) + 1j * 0.03
p_ave = -polariz_freq_osc_strength(
gto_td.e, gto_td.oscillator_strength(), omegas).imag
data = np.array([omegas.real * HARTREE2EV, p_ave])
np.savetxt('test_0153_bse_h2b_uks_rpa_pyscf.txt',
data.T,
fmt=['%f', '%f'])
data_ref = np.loadtxt('test_0153_bse_h2b_uks_rpa_pyscf.txt-ref').T
self.assertTrue(np.allclose(data_ref, data, atol=1e-6, rtol=1e-3))
nao_td = bse_iter(mf=gto_mf, gto=mol, verbosity=0, xc_code='RPA')
polariz = -nao_td.comp_polariz_inter_ave(omegas).imag
data = np.array([omegas.real * HARTREE2EV, polariz])
np.savetxt('test_0153_bse_h2b_uks_rpa_nao.txt',
data.T,
fmt=['%f', '%f'])
data_ref = np.loadtxt('test_0153_bse_h2b_uks_rpa_nao.txt-ref').T
self.assertTrue(np.allclose(data_ref, data, atol=1e-6, rtol=1e-3))
def test_0163_bse_h2o_spin2_uhf_rpa(self):
""" This """
mol = gto.M(verbose=1,atom='O 0 0 0; H 0 0.489 1.074; H 0 0.489 -1.074',basis='cc-pvdz',spin=2)
gto_mf = scf.UKS(mol)
gto_mf.xc = 'hf'
gto_mf.kernel()
gto_td = tddft.dRPA(gto_mf)
gto_td.nstates = 190
gto_td.kernel()
omegas = np.arange(0.0, 2.0, 0.01) + 1j*0.03
p_ave = -polariz_freq_osc_strength(gto_td.e, gto_td.oscillator_strength(), omegas).imag
data = np.array([omegas.real*HARTREE2EV, p_ave])
np.savetxt('test_0163_bse_h2o_spin2_uhf_rpa_pyscf.txt', data.T, fmt=['%f','%f'])
data_ref = np.loadtxt('test_0163_bse_h2o_spin2_uhf_rpa_pyscf.txt-ref').T
self.assertTrue(np.allclose(data_ref, data, atol=1e-6, rtol=1e-3))
nao_td = bse_iter(mf=gto_mf, gto=mol, verbosity=0, xc_code='RPA')
polariz = -nao_td.comp_polariz_inter_ave(omegas).imag
data = np.array([omegas.real*HARTREE2EV, polariz])
np.savetxt('test_0163_bse_h2o_spin2_uhf_rpa_nao.txt', data.T, fmt=['%f','%f'])
data_ref = np.loadtxt('test_0163_bse_h2o_spin2_uhf_rpa_nao.txt-ref').T
self.assertTrue(np.allclose(data_ref, data, atol=1e-5, rtol=1e-3), \
msg="{}".format(abs(data_ref-data).sum()/data.size))
def test_0146_bse_h2o_rhf_rpa(self):
""" Interacting case """
mol = gto.M(
verbose=0,
atom='O 0 0 0;H 0 0.489 1.074;H 0 0.489 -1.074',
basis='cc-pvdz',
)
gto_hf = scf.RKS(mol)
gto_hf.xc = 'hf'
gto_hf.kernel()
gto_td = tddft.dRPA(gto_hf)
gto_td.nstates = 95
gto_td.kernel()
omegas = np.arange(0.0, 2.0, 0.01) + 1j * 0.03
#p_ave = -polariz_inter_ave(gto_hf, mol, gto_td, omegas).imag
p_ave = -polariz_freq_osc_strength(
gto_td.e, gto_td.oscillator_strength(), omegas).imag
data = np.array([omegas.real * HARTREE2EV, p_ave])
np.savetxt('test_0146_bse_h2o_rhf_rpa_pyscf.txt',
data.T,
fmt=['%f', '%f'])
data_ref = np.loadtxt('test_0146_bse_h2o_rhf_rpa_pyscf.txt-ref').T
self.assertTrue(np.allclose(data_ref, data, atol=1e-6, rtol=1e-3))
nao_td = bse_iter(mf=gto_hf, gto=mol, verbosity=0, xc_code='RPA')
p_iter = -nao_td.comp_polariz_inter_ave(omegas).imag
data = np.array([omegas.real * HARTREE2EV, p_iter])
np.savetxt('test_0146_bse_h2o_rhf_rpa_nao.txt',
data.T,
fmt=['%f', '%f'])
data_ref = np.loadtxt('test_0146_bse_h2o_rhf_rpa_nao.txt-ref').T
self.assertTrue(np.allclose(data_ref, data, atol=1e-6, rtol=1e-3))
def test_nao_in_tdscf(self):
""" Attempt to use algorithms implemented in PySCF for diagonalizing the RPA Hamiltonian """
from pyscf import gto, tddft, scf
from pyscf.tdscf.rhf import TDA
mol = gto.M(
verbose=2,
atom='''H 0.0 0.0 -0.3707; H 0.0 0.0 0.3707''',
basis='cc-pvdz',
)
gto_hf = scf.RKS(mol)
gto_hf.xc = 'hf'
gto_hf.kernel()
nocc = mol.nelectron // 2
nmo = gto_hf.mo_energy.size
nvir = nmo - nocc
gto_td = tddft.dRPA(gto_hf)
gto_td.nstates = min(100, nocc * nvir)
gto_td.kernel()
gto_gw = GW(gto_hf, gto_td)
gto_gw.kernel()
ww = np.arange(0.0, 4.0, 0.01) + 1j * 0.02
pxx_xpy = -polariz_inter_xx(gto_hf, mol, gto_td, ww).imag
data = np.array([ww.real * 27.2114, pxx_xpy])
fname = dname + '/h2_rpa_xpy_0099.omega.inter.pxx.txt'
np.savetxt(fname, data.T, fmt=['%f', '%f'])
gw_nao = gw(gto=mol, mf=gto_hf, tdscf=gto_td)
gw_nao.chkfile = None
def test_nao_in_gw_pyscf(self):
""" This is interacting polarizability with SIESTA starting point """
from pyscf import gto, tddft, scf
mol = gto.M( verbose = 0,
atom = '''H 0.0 0.0 -0.3707; H 0.0 0.0 0.3707''', basis = 'cc-pvdz',)
gto_hf = scf.RKS(mol)
gto_hf.xc = 'hf'
gto_hf.kernel()
nocc = mol.nelectron//2
nmo = gto_hf.mo_energy.size
nvir = nmo-nocc
gto_td = tddft.dRPA(gto_hf)
gto_td.nstates = min(100, nocc*nvir)
gto_td.kernel()
gto_gw = GW(gto_hf, gto_td)
gto_gw.kernel()
ww = np.arange(0.0,4.0,0.01)+1j*0.02
pxx_xpy = -polariz_inter_xx(gto_hf, mol, gto_td, ww).imag
data = np.array([ww.real*27.2114, pxx_xpy])
fname = dname+'/h2_rpa_xpy_0098.omega.inter.pxx.txt'
np.savetxt(fname, data.T, fmt=['%f','%f'])
data_ref = np.loadtxt(fname+'-ref')
self.assertTrue(np.allclose(data_ref,data.T, rtol=0.1, atol=1e-05))
gw_nao = gw(gto=mol, mf=gto_hf, tdscf=gto_td)
x = gw_nao.moms1[:,0]
rf_nao = gw_nao.rf( ww )
pxx_nao = np.einsum('p,wpq,q->w', x, -rf_nao.imag, x)
data = np.array([ww.real*27.2114, pxx_nao])
fname = dname+'/h2_rpa_nao_0098.omega.inter.pxx.txt'
np.savetxt(fname, data.T, fmt=['%f','%f'])
data_ref = np.loadtxt(fname+'-ref')
self.assertTrue(np.allclose(data_ref,data.T, rtol=0.1, atol=1e-05))
rf_gto = gw_nao.rf_pyscf( ww )
pxx_gto = np.einsum('p,wpq,q->w', x, -rf_gto.imag, x)
data = np.array([ww.real*27.2114, pxx_gto])
fname = dname+'/h2_rpa_gto_0098.omega.inter.pxx.txt'
np.savetxt(fname, data.T, fmt=['%f','%f'])
data_ref = np.loadtxt(fname+'-ref')
self.assertTrue(np.allclose(data_ref,data.T, rtol=0.1, atol=1e-05))
def test_qchem_irf(self):
""" Test """
gto_hf = dft.RKS(mol)
gto_hf.kernel()
nocc = mol.nelectron//2
nmo = gto_hf.mo_energy.size
nvir = nmo-nocc
gto_td = tddft.dRPA(gto_hf)
gto_td.nstates = min(100, nocc*nvir)
gto_td.kernel()
gto_gw = GW(gto_hf, gto_td)
gto_gw.kernel()
nao_td = tddft_iter(mf=gto_hf, gto=mol, xc_code='RPA')
eps = 0.02
omegas = np.arange(0.0,2.0,eps/2.0)+1j*eps
p_iter = -nao_td.comp_polariz_inter_ave(omegas).imag
data = np.array([omegas.real*27.2114, p_iter])
np.savetxt('NH.tddft_iter_rpa.omega.inter.pav.txt', data.T, fmt=['%f','%f'])
np.set_printoptions(linewidth=180)
def test_qchem_irf(self):
""" Test """
gto_hf = dft.RKS(mol)
gto_hf.kernel()
nocc = mol.nelectron // 2
nmo = gto_hf.mo_energy.size
nvir = nmo - nocc
gto_td = tddft.dRPA(gto_hf)
gto_td.nstates = min(100, nocc * nvir)
gto_td.kernel()
gto_gw = GW(gto_hf, gto_td)
gto_gw.kernel()
nao_td = tddft_iter(mf=gto_hf, gto=mol, xc_code='RPA')
eps = 0.02
omegas = np.arange(0.0, 2.0, eps / 2.0) + 1j * eps
p_iter = -nao_td.comp_polariz_inter_ave(omegas).imag
data = np.array([omegas.real * 27.2114, p_iter])
np.savetxt('NH.tddft_iter_rpa.omega.inter.pav.txt',
data.T,
fmt=['%f', '%f'])
np.set_printoptions(linewidth=180)
mol = gto.Mole()
mol.verbose = 5
mol.atom = [[8, (0., 0., 0.)], [1, (0., -0.757, 0.587)],
[1, (0., 0.757, 0.587)]]
mol.basis = 'cc-pvdz'
mol.build()
mf = dft.RKS(mol)
mf.xc = 'hf'
mf.kernel()
nocc = mol.nelectron // 2
nmo = mf.mo_energy.size
nvir = nmo - nocc
td = tddft.dRPA(mf)
td.nstates = min(100, nocc * nvir)
td.kernel()
gw = GW(mf, td)
gw.kernel()
print(gw.mo_energy)
# [-20.10555946 -1.2264067 -0.68160939 -0.53066326 -0.44679868
# 0.17291986 0.24457082 0.74758227 0.80045129 1.11748735
# 1.1508353 1.19081928 1.40406947 1.43593681 1.63324734
# 1.81839838 1.86943727 2.37827782 2.48829939 3.26028229
# 3.3247595 3.4958492 3.77735135 4.14572189]
gw.linearized = True
gw.kernel(orbs=[nocc - 1, nocc])
print(gw.mo_energy[nocc - 1] - -0.44684106)
mol.atom = [
[8 , (0. , 0. , 0.)],
[1 , (0. , -0.757 , 0.587)],
[1 , (0. , 0.757 , 0.587)]]
mol.basis = 'cc-pvdz'
mol.build()
mf = dft.RKS(mol)
mf.xc = 'hf'
mf.kernel()
nocc = mol.nelectron//2
nmo = mf.mo_energy.size
nvir = nmo-nocc
td = tddft.dRPA(mf)
td.nstates = min(100, nocc*nvir)
td.kernel()
gw = GW(mf, td)
gw.kernel()
print(gw.mo_energy)
# [-20.10555946 -1.2264067 -0.68160939 -0.53066326 -0.44679868
# 0.17291986 0.24457082 0.74758227 0.80045129 1.11748735
# 1.1508353 1.19081928 1.40406947 1.43593681 1.63324734
# 1.81839838 1.86943727 2.37827782 2.48829939 3.26028229
# 3.3247595 3.4958492 3.77735135 4.14572189]
gw.linearized = True
gw.kernel(orbs=[nocc-1,nocc])
print(gw.mo_energy[nocc-1] - -0.44684106)
mol.basis = 'aug-cc-pvtz'
mol.build()
def diagonalize(a, b):
nocc, nvir = a.shape[:2]
aa = a.reshape(nocc * nvir, nocc * nvir)
bb = b.reshape(nocc * nvir, nocc * nvir)
e = numpy.linalg.eig(numpy.bmat([[aa, bb], [-bb.conj(), -aa.conj()]]))[0]
e = numpy.sort(e[e > 0])
return e
nroots = 5
mf = dft.RKS(mol)
mf.xc = 'pbe,pbe'
mf.kernel()
a, b = tddft.dRPA(mf).get_ab()
e = diagonalize(a, b)
print('dTD:', e[:nroots])
nocc, nvir = a.shape[:2]
a = a.reshape(nocc * nvir, nocc * nvir)
etda = numpy.linalg.eig(a)[0]
etda = numpy.sort(etda)
print('dTDA:', etda[:nroots])
e_corr = 0.5 * sum(e - etda)
print('dRPA correlation energy', e_corr)