def test_energy_hydrogen():
fn_fchk = context.get_fn('test/h_sto3g.fchk')
mol = IOData.from_file(fn_fchk)
kin = mol.obasis.compute_kinetic(mol.lf)
na = mol.obasis.compute_nuclear_attraction(mol.coordinates, mol.pseudo_numbers, mol.lf)
er = mol.obasis.compute_electron_repulsion(mol.lf)
terms = [
UTwoIndexTerm(kin, 'kin'),
UDirectTerm(er, 'hartree'),
UExchangeTerm(er, 'x_hf'),
UTwoIndexTerm(na, 'ne'),
]
external = {'nn': compute_nucnuc(mol.coordinates, mol.pseudo_numbers)}
ham = UEffHam(terms, external)
helper_compute(ham, mol.lf, mol.exp_alpha, mol.exp_beta)
assert abs(ham.cache['energy'] - -4.665818503844346E-01) < 1e-8
def test_energy_hydrogen():
fn_fchk = context.get_fn('test/h_sto3g.fchk')
mol = IOData.from_file(fn_fchk)
kin = mol.obasis.compute_kinetic(mol.lf)
na = mol.obasis.compute_nuclear_attraction(mol.coordinates,
mol.pseudo_numbers, mol.lf)
er = mol.obasis.compute_electron_repulsion(mol.lf)
terms = [
UTwoIndexTerm(kin, 'kin'),
UDirectTerm(er, 'hartree'),
UExchangeTerm(er, 'x_hf'),
UTwoIndexTerm(na, 'ne'),
]
external = {'nn': compute_nucnuc(mol.coordinates, mol.pseudo_numbers)}
ham = UEffHam(terms, external)
helper_compute(ham, mol.lf, mol.exp_alpha, mol.exp_beta)
assert abs(ham.cache['energy'] - -4.665818503844346E-01) < 1e-8
def test_project_msg_larger():
# Load STO3G system and keep essential results
mol = IOData.from_file(context.get_fn('test/water_sto3g_hf_g03.fchk'))
obasis0 = mol.obasis
exp0 = mol.exp_alpha
# Upgrade the basis to 3-21G and project
obasis1 = get_gobasis(mol.coordinates, mol.numbers, '3-21G')
lf1 = DenseLinalgFactory(obasis1.nbasis)
exp1 = lf1.create_expansion()
project_orbitals_mgs(obasis0, obasis1, exp0, exp1)
assert (exp1.energies == 0.0).all()
assert exp0.occupations.sum() == exp1.occupations.sum()
assert (exp1.coeffs[:, 5:] == 0.0).all()
# Check the normalization of the projected orbitals
olp = obasis1.compute_overlap(lf1)
exp1.check_orthonormality(olp)
# Setup HF hamiltonian and compute energy
kin = obasis1.compute_kinetic(lf1)
na = obasis1.compute_nuclear_attraction(mol.coordinates,
mol.pseudo_numbers, lf1)
er = obasis1.compute_electron_repulsion(lf1)
terms = [
RTwoIndexTerm(kin, 'kin'),
RDirectTerm(er, 'hartree'),
RExchangeTerm(er, 'x_hf'),
RTwoIndexTerm(na, 'ne'),
]
ham = REffHam(terms)
# Compute energy after projection
energy1 = helper_compute(ham, lf1, exp1)[0]
# Optimize wfn
scf_solver = PlainSCFSolver(1e-6)
occ_model = AufbauOccModel(5)
scf_solver(ham, lf1, olp, occ_model, exp1)
energy2 = ham.cache['energy']
assert energy2 < energy1 # the energy should decrease after scf convergence
# Construct a core initial guess
guess_core_hamiltonian(olp, kin, na, exp1)
energy3 = helper_compute(ham, lf1, exp1)[0]
assert energy3 > energy1 # the projected guess should be better than the core guess
def test_project_msg_larger():
# Load STO3G system and keep essential results
mol = IOData.from_file(context.get_fn('test/water_sto3g_hf_g03.fchk'))
obasis0 = mol.obasis
exp0 = mol.exp_alpha
# Upgrade the basis to 3-21G and project
obasis1 = get_gobasis(mol.coordinates, mol.numbers, '3-21G')
lf1 = DenseLinalgFactory(obasis1.nbasis)
exp1 = lf1.create_expansion()
project_orbitals_mgs(obasis0, obasis1, exp0, exp1)
assert (exp1.energies == 0.0).all()
assert exp0.occupations.sum() == exp1.occupations.sum()
assert (exp1.coeffs[:,5:] == 0.0).all()
# Check the normalization of the projected orbitals
olp = obasis1.compute_overlap(lf1)
exp1.check_orthonormality(olp)
# Setup HF hamiltonian and compute energy
kin = obasis1.compute_kinetic(lf1)
na = obasis1.compute_nuclear_attraction(mol.coordinates, mol.pseudo_numbers, lf1)
er = obasis1.compute_electron_repulsion(lf1)
terms = [
RTwoIndexTerm(kin, 'kin'),
RDirectTerm(er, 'hartree'),
RExchangeTerm(er, 'x_hf'),
RTwoIndexTerm(na, 'ne'),
]
ham = REffHam(terms)
# Compute energy after projection
energy1 = helper_compute(ham, lf1, exp1)[0]
# Optimize wfn
scf_solver = PlainSCFSolver(1e-6)
occ_model = AufbauOccModel(5)
scf_solver(ham, lf1, olp, occ_model, exp1)
energy2 = ham.cache['energy']
assert energy2 < energy1 # the energy should decrease after scf convergence
# Construct a core initial guess
guess_core_hamiltonian(olp, kin, na, exp1)
energy3 = helper_compute(ham, lf1, exp1)[0]
assert energy3 > energy1 # the projected guess should be better than the core guess
def test_project_msg_smaller():
# Load 3-21G system and keep essential results
mol = IOData.from_file(context.get_fn('test/li_h_3-21G_hf_g09.fchk'))
obasis0 = mol.obasis
exp0_alpha = mol.exp_alpha
exp0_beta = mol.exp_beta
# Downgrade the basis to sto-3g and project
obasis1 = get_gobasis(mol.coordinates, mol.numbers, 'sto-3g')
lf1 = DenseLinalgFactory(obasis1.nbasis)
exp1_alpha = lf1.create_expansion()
exp1_beta = lf1.create_expansion()
project_orbitals_mgs(obasis0, obasis1, exp0_alpha, exp1_alpha)
project_orbitals_mgs(obasis0, obasis1, exp0_beta, exp1_beta)
assert (exp1_alpha.energies == 0.0).all()
assert (exp1_beta.energies == 0.0).all()
assert exp1_alpha.occupations.sum() == 2
assert exp1_beta.occupations.sum() == 1
assert (exp1_alpha.coeffs[:, 2:] == 0.0).all()
assert (exp1_beta.coeffs[:, 1:] == 0.0).all()
# Check the normalization of the projected orbitals
olp = obasis1.compute_overlap(lf1)
exp1_alpha.check_orthonormality(olp)
exp1_beta.check_orthonormality(olp)
# Setup HF hamiltonian and compute energy
kin = obasis1.compute_kinetic(lf1)
na = obasis1.compute_nuclear_attraction(mol.coordinates,
mol.pseudo_numbers, lf1)
er = obasis1.compute_electron_repulsion(lf1)
terms = [
UTwoIndexTerm(kin, 'kin'),
UDirectTerm(er, 'hartree'),
UExchangeTerm(er, 'x_hf'),
UTwoIndexTerm(na, 'ne'),
]
ham = UEffHam(terms)
# Compute energy before SCF
energy1 = helper_compute(ham, lf1, exp1_alpha, exp1_beta)[0]
scf_solver = PlainSCFSolver(1e-6)
occ_model = AufbauOccModel(2, 1)
scf_solver(ham, lf1, olp, occ_model, exp1_alpha, exp1_beta)
energy2 = ham.cache['energy']
assert energy2 < energy1 # the energy should decrease after scf convergence
def test_project_msg_smaller():
# Load 3-21G system and keep essential results
mol = IOData.from_file(context.get_fn('test/li_h_3-21G_hf_g09.fchk'))
obasis0 = mol.obasis
exp0_alpha = mol.exp_alpha
exp0_beta = mol.exp_beta
# Downgrade the basis to sto-3g and project
obasis1 = get_gobasis(mol.coordinates, mol.numbers, 'sto-3g')
lf1 = DenseLinalgFactory(obasis1.nbasis)
exp1_alpha = lf1.create_expansion()
exp1_beta = lf1.create_expansion()
project_orbitals_mgs(obasis0, obasis1, exp0_alpha, exp1_alpha)
project_orbitals_mgs(obasis0, obasis1, exp0_beta, exp1_beta)
assert (exp1_alpha.energies == 0.0).all()
assert (exp1_beta.energies == 0.0).all()
assert exp1_alpha.occupations.sum() == 2
assert exp1_beta.occupations.sum() == 1
assert (exp1_alpha.coeffs[:,2:] == 0.0).all()
assert (exp1_beta.coeffs[:,1:] == 0.0).all()
# Check the normalization of the projected orbitals
olp = obasis1.compute_overlap(lf1)
exp1_alpha.check_orthonormality(olp)
exp1_beta.check_orthonormality(olp)
# Setup HF hamiltonian and compute energy
kin = obasis1.compute_kinetic(lf1)
na = obasis1.compute_nuclear_attraction(mol.coordinates, mol.pseudo_numbers, lf1)
er = obasis1.compute_electron_repulsion(lf1)
terms = [
UTwoIndexTerm(kin, 'kin'),
UDirectTerm(er, 'hartree'),
UExchangeTerm(er, 'x_hf'),
UTwoIndexTerm(na, 'ne'),
]
ham = UEffHam(terms)
# Compute energy before SCF
energy1 = helper_compute(ham, lf1, exp1_alpha, exp1_beta)[0]
scf_solver = PlainSCFSolver(1e-6)
occ_model = AufbauOccModel(2, 1)
scf_solver(ham, lf1, olp, occ_model, exp1_alpha, exp1_beta)
energy2 = ham.cache['energy']
assert energy2 < energy1 # the energy should decrease after scf convergence
