def test_natorbs_fclist(self):
for arr in self.mf.mo_coeff.T, self.mf.mo_occ, self.mf.mo_energy:
arr[[0, 5]] = arr[[5, 0]]
arr[[1, 3]] = arr[[3, 1]]
mol = self.mf.mol
with DFMP2(self.mf, frozen=[3, 5]) as pt:
# also check the density matrix
rdm1 = pt.make_rdm1()
self.assertAlmostEqual(rdm1[3, 3], 2.0, delta=1.0e-12)
self.assertAlmostEqual(rdm1[5, 5], 2.0, delta=1.0e-12)
# now calculate the natural orbitals
natocc, natorb = pt.make_natorbs()
# number of electrons conserved
self.assertAlmostEqual(numpy.sum(natocc),
mol.nelectron,
delta=1.0e-10)
# orbitals orthogonal
check_orth(self, mol, natorb)
# selected values
self.assertAlmostEqual(natocc[0], 2.0, delta=1.0e-12)
self.assertAlmostEqual(natocc[1], 2.0, delta=1.0e-12)
self.assertAlmostEqual(natocc[2], 1.9832413380, delta=1.0e-7)
self.assertAlmostEqual(natocc[7], 1.9384836199, delta=1.0e-7)
self.assertAlmostEqual(natocc[8], 0.0459325459, delta=1.0e-7)
self.assertAlmostEqual(natocc[47], 0.0000751662, delta=1.0e-7)
def test_energy_fclist(self):
for arr in self.mf.mo_coeff.T, self.mf.mo_occ, self.mf.mo_energy:
arr[[0, 2]] = arr[[2, 0]]
arr[[1, 6]] = arr[[6, 1]]
with DFMP2(self.mf, frozen=[2, 6]) as pt:
pt.kernel()
self.assertAlmostEqual(pt.e_corr, -0.274767743344, delta=1.0e-8)
self.assertAlmostEqual(pt.e_tot, -78.252218528769, delta=1.0e-8)
def test_natorbs(self):
mol = self.mf.mol
with DFMP2(self.mf) as pt:
natocc, natorb = pt.make_natorbs()
# number of electrons conserved
self.assertAlmostEqual(numpy.sum(natocc),
mol.nelectron,
delta=1.0e-10)
# orbitals orthogonal
check_orth(self, mol, natorb)
# selected values
self.assertAlmostEqual(natocc[0], 1.9997941377, delta=1.0e-7)
self.assertAlmostEqual(natocc[7], 1.9384231532, delta=1.0e-7)
self.assertAlmostEqual(natocc[8], 0.0459829060, delta=1.0e-7)
self.assertAlmostEqual(natocc[47], 0.0000761012, delta=1.0e-7)
def test_natorbs_relaxed_fc(self):
mol = self.mf.mol
with DFMP2(self.mf, frozen=2) as pt:
pt.cphf_tol = 1e-12
natocc, natorb = pt.make_natorbs(relaxed=True)
# number of electrons conserved
self.assertAlmostEqual(numpy.sum(natocc),
mol.nelectron,
delta=1.0e-10)
# orbitals orthogonal
check_orth(self, mol, natorb)
# selected values
self.assertAlmostEqual(natocc[0], 2.0000042719, delta=1.0e-7)
self.assertAlmostEqual(natocc[7], 1.9402389041, delta=1.0e-7)
self.assertAlmostEqual(natocc[8], 0.0459325459, delta=1.0e-7)
self.assertAlmostEqual(natocc[47], 0.0000652683, delta=1.0e-7)
def test_natorbs_relaxed(self):
mol = self.mf.mol
with DFMP2(self.mf) as pt:
pt.cphf_tol = 1e-12
natocc, natorb = pt.make_natorbs(relaxed=True)
# number of electrons conserved
self.assertAlmostEqual(numpy.sum(natocc),
mol.nelectron,
delta=1.0e-10)
# orbitals orthogonal
check_orth(self, mol, natorb)
# selected values
self.assertAlmostEqual(natocc[0], 1.9997950023, delta=1.0e-7)
self.assertAlmostEqual(natocc[7], 1.9402044334, delta=1.0e-7)
self.assertAlmostEqual(natocc[8], 0.0459829060, delta=1.0e-7)
self.assertAlmostEqual(natocc[47], 0.0000658464, delta=1.0e-7)
def test_natorbs_fc(self):
mol = self.mf.mol
with DFMP2(self.mf, frozen=2) as pt:
natocc, natorb = pt.make_natorbs()
# number of electrons conserved
self.assertAlmostEqual(numpy.sum(natocc),
mol.nelectron,
delta=1.0e-10)
# orbitals orthogonal
check_orth(self, mol, natorb)
# selected values
self.assertAlmostEqual(natocc[0], 2.0, delta=1.0e-12)
self.assertAlmostEqual(natocc[1], 2.0, delta=1.0e-12)
self.assertAlmostEqual(natocc[2], 1.9832413380, delta=1.0e-7)
self.assertAlmostEqual(natocc[7], 1.9384836199, delta=1.0e-7)
self.assertAlmostEqual(natocc[8], 0.0459325459, delta=1.0e-7)
self.assertAlmostEqual(natocc[47], 0.0000751662, delta=1.0e-7)
def test_natorbs_relaxed_fclist(self):
for arr in self.mf.mo_coeff.T, self.mf.mo_occ, self.mf.mo_energy:
arr[[0, 2]] = arr[[2, 0]]
arr[[1, 6]] = arr[[6, 1]]
mol = self.mf.mol
with DFMP2(self.mf, frozen=[2, 6]) as pt:
pt.cphf_tol = 1e-12
natocc, natorb = pt.make_natorbs(relaxed=True)
# number of electrons conserved
self.assertAlmostEqual(numpy.sum(natocc),
mol.nelectron,
delta=1.0e-10)
# orbitals orthogonal
check_orth(self, mol, natorb)
# selected values
self.assertAlmostEqual(natocc[0], 2.0000042719, delta=1.0e-7)
self.assertAlmostEqual(natocc[7], 1.9402389041, delta=1.0e-7)
self.assertAlmostEqual(natocc[8], 0.0459325459, delta=1.0e-7)
self.assertAlmostEqual(natocc[47], 0.0000652683, delta=1.0e-7)
def test_energy_fc(self):
with DFMP2(self.mf, frozen=2) as pt:
pt.kernel()
self.assertAlmostEqual(pt.e_corr, -0.274767743344, delta=1.0e-8)
self.assertAlmostEqual(pt.e_tot, -78.252218528769, delta=1.0e-8)
def test_energy(self):
with DFMP2(self.mf) as pt:
pt.kernel()
self.assertAlmostEqual(pt.e_corr, -0.280727901936, delta=1.0e-8)
self.assertAlmostEqual(pt.e_tot, -78.258178687361, delta=1.0e-8)
from pyscf.scf import RHF
from pyscf.mp.dfmp2_native import DFMP2
mol = Mole()
mol.atom = '''
C 0.000000 0.000000 0.000000
Cl 0.000000 0.000000 1.785000
H 1.019297 0.000000 -0.386177
H -0.509649 0.882737 -0.386177
H -0.509649 -0.882737 -0.386177
'''
mol.basis = 'aug-cc-pVTZ'
mol.build()
mf = RHF(mol).run()
pt = DFMP2(mf).run()
# The unrelaxed density always has got natural occupation numbers between 2 and 0.
# However, it is inaccurate for properties.
dm_ur = pt.make_rdm1_unrelaxed(ao_repr=True)
# The relaxed density is more accurate for properties when MP2 is well-behaved,
# whereas the natural occupation numbers can be above 2 or below 0 for ill-behaved systems.
dm_re = pt.make_rdm1_relaxed(ao_repr=True)
print('')
print('HF dipole moment:')
dip = mf.dip_moment() # 2.10
print('Absolute value: {0:.3f} Debye'.format(norm(dip)))
print('')
