def test_fci_rdms_1():
"""Test the FCI 2- and 3-RDMs on LiH/STO-3G"""
# setup job
xyz = """
Li
H 1 3.0
units bohr
"""
input = solver_factory(molecule=xyz, basis='sto-3g')
state = input.state(charge=0, multiplicity=1, sym='a1')
hf = HF(input, state=state)
fci = ActiveSpaceSolver(hf, type='FCI', states=state, options={'fci_test_rdms': True})
fci.run()
# check results
print("Testing AAAA 2-RDM")
assert psi4.core.variable("AAAA 2-RDM ERROR") == pytest.approx(0.0, 1.0e-10)
print("Testing BBBB 2-RDM")
assert psi4.core.variable("BBBB 2-RDM ERROR") == pytest.approx(0.0, 1.0e-10)
print("Testing ABAB 2-RDM")
assert psi4.core.variable("ABAB 2-RDM ERROR") == pytest.approx(0.0, 1.0e-10)
print("Testing AAAAAA 3-RDM")
assert psi4.core.variable("AAAAAA 3-RDM ERROR") == pytest.approx(0.0, 1.0e-10)
print("Testing AABAAB 3-RDM")
assert psi4.core.variable("AABAAB 3-RDM ERROR") == pytest.approx(0.0, 1.0e-10)
print("Testing ABBABB 3-RDM")
assert psi4.core.variable("ABBABB 3-RDM ERROR") == pytest.approx(0.0, 1.0e-10)
print("Testing BBBBBB 3-RDM")
assert psi4.core.variable("BBBBBB 3-RDM ERROR") == pytest.approx(0.0, 1.0e-10)
def test_uhf():
"""Test UHF computation of the B1 state of methylene."""
ref_energy = -38.92655952236967
# create a molecule from a string
mol = Molecule.from_geom("""
C
H 1 1.085
H 1 1.085 2 135.5
""")
# create a basis object
basis = Basis('cc-pVDZ')
# create a molecular model
input = solver_factory(molecule=mol, basis=basis)
# specify the electronic state
state = input.state(charge=0, multiplicity=3, sym='b1')
# define a HF object
hf = HF(input, state=state, restricted=False)
hf.run()
assert hf.value('hf energy') == pytest.approx(ref_energy, 1.0e-10)
def test_solver_2():
"""Test RHF on H2."""
# define a molecule
xyz = """
H 0.0 0.0 0.0
H 0.0 0.0 1.0
"""
# create a molecular model
input = solver_factory(molecule=xyz, basis='cc-pVDZ')
# specify the electronic state
state = input.state(charge=0, multiplicity=1, sym='ag')
# create a HF object and run
hf = HF(input, state=state)
fci = ActiveSpaceSolver(hf, state, 'FCI')
spin = SpinAnalysis(fci)
test_graph = """SpinAnalysis
|
ActiveSpaceSolver
|
HF
|
Input"""
assert spin.computational_graph() == test_graph
def test_uhf_wrong_sym():
"""Test UHF computation that lands on the wrong symmetry state."""
# create a molecule from a string
mol = Molecule.from_geom("""
C
H 1 1.085
H 1 1.085 2 135.5
""")
# create a basis object
basis = Basis('cc-pVDZ')
# create a molecular model
input = solver_factory(molecule=mol, basis=basis)
# specify the electronic state
state = input.state(charge=0, multiplicity=3, sym='a1')
# define a HF object
hf = HF(input, state=state, docc=[2, 0, 0, 1], socc=[1, 0, 1, 0], restricted=False)
# should raise an error since we get a state with different symmetry
with pytest.raises(RuntimeError):
hf.run()
def test_rhf_docc():
"""Test RHF on LiH using an occupation pattern that is not optimal.
This example shows an alternative way to build the molecule/basis."""
ref_energy = -7.40425598707951
# create a molecule from a string
mol = Molecule.from_geom("""
Li 0.0 0.0 0.0
H 0.0 0.0 1.6
""")
# create a basis object
basis = Basis('cc-pVDZ')
# create a molecular model
input = solver_factory(molecule=mol, basis=basis)
# specify the electronic state
state = input.state(charge=0, multiplicity=1, sym='a1')
hf = HF(input, state=state, docc=[1, 0, 1, 0])
hf.run()
assert hf.value('hf energy') == pytest.approx(ref_energy, 1.0e-10)
def test_detci_2():
"""Test GAS CI calculation with multi-gas algorithm"""
ref_hf_energy = -76.0172965561
ref_gas1_energy = -76.029945793736
ref_gas2_energy = -55.841944166803
# setup job
xyz = """
O
H 1 1.00
H 1 1.00 2 103.1
"""
input = solver_factory(molecule=xyz, basis='6-31g**')
state = input.state(charge=0, multiplicity=1, sym='a1')
hf = HF(input, state=state, d_convergence=1.0e-10)
hf.run()
# define two states with different number of GAS constraints
gas_state_1 = input.state(charge=0, multiplicity=1, sym='a1', gasmin=[0], gasmax=[2])
gas_state_2 = input.state(charge=0, multiplicity=1, sym='a1', gasmin=[0], gasmax=[1])
# define the active space
mo_spaces = input.mo_spaces(gas1=[1, 0, 0, 0], gas2=[3, 0, 1, 2])
# create a detci solver
fci = ActiveSpaceSolver(
hf, type='detci', states=[gas_state_1, gas_state_2], mo_spaces=mo_spaces, options={'active_ref_type': 'gas'}
)
fci.run()
# check results
assert hf.value('hf energy') == pytest.approx(ref_hf_energy, 1.0e-10)
assert fci.value('active space energy')[gas_state_1] == pytest.approx([ref_gas1_energy], 1.0e-10)
assert fci.value('active space energy')[gas_state_2] == pytest.approx([ref_gas2_energy], 1.0e-10)
def test_detci_4():
"""CASCI test of Forte DETCI using the SparseList algorithm to build the sigma vector"""
ref_hf_energy = -99.977636678461636
ref_fci_energy = -100.113732484560970
xyz = """
F
H 1 1.0
"""
input = solver_factory(molecule=xyz, basis='6-31g')
state = input.state(charge=0, multiplicity=1, sym='a1')
hf = HF(input, state=state, e_convergence=1.0e-12, d_convergence=1.0e-8)
# create a detci solver
fci = ActiveSpaceSolver(
hf,
type='detci',
states=state,
mo_spaces=input.mo_spaces(frozen_docc=[1, 0, 0, 0]),
options={'active_ref_type': 'cas'})
fci.run()
# check results
assert hf.value('hf energy') == pytest.approx(ref_hf_energy, 1.0e-10)
assert fci.value('active space energy')[state] == pytest.approx(
[ref_fci_energy], 1.0e-10)
def test_aci_1():
"""Test FCI on Li2/STO-3G. Reproduces the test aci-1"""
ref_hf_energy = -14.839846512738
ref_aci_energy = -14.889166993726
# setup job
xyz = """
Li
Li 1 2.0
"""
input = solver_factory(molecule=xyz, basis='DZ')
state = input.state(charge=0, multiplicity=1, sym='ag')
hf = HF(input, state=state)
options = {
'sigma': 0.001,
'sci_enforce_spin_complete': False,
'sci_project_out_spin_contaminants': False,
'active_ref_type': 'hf'
}
aci = ActiveSpaceSolver(hf, type='ACI', states=state, options=options)
aci.run()
# check results
assert hf.value('hf energy') == pytest.approx(ref_hf_energy, 1.0e-10)
assert aci.value('active space energy')[state] == pytest.approx(
[ref_aci_energy], 1.0e-10)
def test_hf_callback():
"""Example of using a callback to localize HF MOs."""
xyz = """
H 0.0 0.0 0.0
H 0.0 0.0 1.0
H 0.0 0.0 2.0
H 0.0 0.0 3.0
symmetry c1
"""
input = solver_factory(molecule=xyz, basis='sto-3g')
state = input.state(charge=0, multiplicity=1)
cbh = CallbackHandler()
def localize(cb, state):
"""Localize the orbitals after a HF computation"""
import psi4
wfn = state.data.psi_wfn
basis_ = wfn.basisset()
C = wfn.Ca_subset("AO", "ALL")
Local = psi4.core.Localizer.build("PIPEK_MEZEY", basis_, C)
Local.localize()
new_C = Local.L
wfn.Ca().copy(new_C)
wfn.Cb().copy(new_C)
cbh.add_callback('post hf', localize)
hf = HF(input, state=state, restricted=False, cbh=cbh)
hf.run()
def test_fci_one_electron():
"""Test FCI on a one-electron system"""
ref_hf_energy = -0.600480545551890
ref_fci_energy = -0.600480545551890
xyz = """
H
H 1 1.0
"""
input = solver_factory(molecule=xyz, basis='aug-cc-pVDZ')
state = input.state(charge=1, multiplicity=2, sym='ag')
hf = HF(input, state=state, e_convergence=1.0e-12)
# define an active space
mo_spaces = input.mo_spaces(frozen_docc=[0, 0, 0, 0, 0, 0, 0, 0],
restricted_docc=[0, 0, 0, 0, 0, 0, 0, 0],
active=[1, 0, 0, 0, 0, 0, 0, 0])
fci = ActiveSpaceSolver(hf,
type='FCI',
states=state,
e_convergence=1.0e-12,
mo_spaces=mo_spaces)
fci.run()
# check results
assert hf.value('hf energy') == pytest.approx(ref_hf_energy, 1.0e-10)
assert fci.value('active space energy')[state] == pytest.approx(
[ref_fci_energy], 1.0e-10)
def test_solver():
"""Test RHF on H2."""
ref_energy = -1.10015376479352
# define a molecule
xyz = """
H 0.0 0.0 0.0
H 0.0 0.0 1.0
"""
# create a molecular model
input = solver_factory(molecule=xyz, basis='cc-pVDZ')
# create a HF object and run
with pytest.raises(AssertionError):
spin = SpinAnalysis(input)
def test_aci_3():
"""Test FCI on H4/STO-3G. Reproduces the test aci-1"""
ref_hf_energy = -2.0310813811962456
ref_aci_energy = -2.115455548674
ref_acipt2_energy = -2.116454734743
spin_val = 1.02027340
# setup job
xyz = """
H -0.4 0.0 0.0
H 0.4 0.0 0.0
H 0.1 -0.3 1.0
H -0.1 0.5 1.0
"""
input = solver_factory(molecule=xyz, basis='cc-pVDZ')
state = input.state(charge=0, multiplicity=1, sym='a')
hf = HF(input, state=state, e_convergence=1.0e-12, d_convergence=1.0e-6)
options = {
'sigma': 0.001,
'active_ref_type': 'hf',
'diag_algorithm': 'SPARSE',
'active_guess_size': 300,
'aci_screen_alg': 'BATCH_HASH',
'aci_nbatch': 2
}
aci = ActiveSpaceSolver(hf,
type='ACI',
states=state,
e_convergence=1.0e-11,
r_convergence=1.0e-7,
options=options)
spin = SpinAnalysis(aci, options={'SPIN_TEST': True})
spin.run()
# check results
assert hf.value('hf energy') == pytest.approx(ref_hf_energy, 1.0e-10)
assert aci.value('active space energy')[state] == pytest.approx(
[ref_aci_energy], 1.0e-9)
assert psi4.core.variable("ACI+PT2 ENERGY") == pytest.approx(
ref_acipt2_energy, 1.0e-8)
assert psi4.core.variable("SPIN CORRELATION TEST") == pytest.approx(
spin_val, 1.0e-7)
def test_fci_ex_1():
"""Test FCI on the ground and first singlet A1 states of acetone"""
ref_hf_energy = -190.88631411404435
ref_fci_energies = [-190.903043353477869, -190.460579059045074]
# setup job
xyz = """
H 0.000000 2.136732 -0.112445
H 0.000000 -2.136732 -0.112445
H -0.881334 1.333733 -1.443842
H 0.881334 -1.333733 -1.443842
H -0.881334 -1.333733 -1.443842
H 0.881334 1.333733 -1.443842
C 0.000000 0.000000 0.000000
C 0.000000 1.287253 -0.795902
C 0.000000 -1.287253 -0.795902
O 0.000000 0.000000 1.227600
units angstrom
"""
input = solver_factory(molecule=xyz, basis='3-21g')
state = input.state(charge=0, multiplicity=1, sym='a1')
hf = HF(input, state=state, docc=[8, 1, 2, 5])
hf.run()
assert hf.value('hf energy') == pytest.approx(ref_hf_energy, 1.0e-10)
# define an active space
mo_spaces = input.mo_spaces(frozen_docc=[3, 0, 0, 1],
restricted_docc=[4, 1, 1, 3],
active=[2, 0, 2, 1])
# compute the FCI energy for the double B1 (M_S = 1/2) solution
fci = ActiveSpaceSolver(hf,
type='FCI',
states={state: 2},
mo_spaces=mo_spaces)
fci.run()
# check results
assert fci.value('active space energy')[state] == pytest.approx(
ref_fci_energies, 1.0e-10)
def test_rhf():
"""Test RHF on H2."""
ref_energy = -1.10015376479352
# define a molecule
xyz = """
H 0.0 0.0 0.0
H 0.0 0.0 1.0
"""
# create a molecular model
input = solver_factory(molecule=xyz, basis='cc-pVDZ')
# specify the electronic state
state = input.state(charge=0, multiplicity=1, sym='ag')
# create a HF object and run
hf = HF(input, state=state)
hf.run()
assert hf.value('hf energy') == pytest.approx(ref_energy, 1.0e-10)
def test_fci_1():
"""Test FCI on Li2/STO-3G"""
ref_hf_energy = -14.54873910108353
ref_fci_energy = -14.595808852754054
# setup job
xyz = """
Li
Li 1 3.0
units bohr
"""
input = solver_factory(molecule=xyz, basis='sto-3g')
state = input.state(charge=0, multiplicity=1, sym='ag')
hf = HF(input, state=state)
fci = ActiveSpaceSolver(hf, type='FCI', states=state)
fci.run()
# check results
assert hf.value('hf energy') == pytest.approx(ref_hf_energy, 1.0e-10)
assert fci.value('active space energy')[state] == pytest.approx(
[ref_fci_energy], 1.0e-10)
def test_df_rhf():
"""Test DF-RHF on HF."""
ref_energy = -100.04775218911111
# define a molecule
xyz = """
H 0.0 0.0 0.0
F 0.0 0.0 1.0
"""
# create a molecular model
input = solver_factory(molecule=xyz, basis='cc-pVTZ', int_type='df')
# specify the electronic state
state = input.state(charge=0, multiplicity=1, sym='a1')
# create a HF object and run
hf = HF(input, state=state)
hf.run()
assert hf.value('hf energy') == pytest.approx(ref_energy, 1.0e-10)
def test_fci_7():
"""
Test FCI on the doublet state of CH and triplet state of CH+.
It also verifies that computations with different values of M_S yield the same energy
"""
ref_hf_energy = -37.43945401822133
ref_fci_energy = -37.49081328115731
# setup job
xyz = """
C
H 1 1.0
units bohr
"""
input = solver_factory(molecule=xyz, basis='6-31G')
state = input.state(charge=0, multiplicity=2, sym='b1')
hf_doublet = HF(input, state=state, docc=[3, 0, 0, 0], socc=[0, 0, 1, 0])
hf_doublet.run()
# compute the FCI energy for the double B1 (M_S = 1/2) solution
state_doublet_1 = input.state(charge=0, multiplicity=2, ms=0.5, sym='b1')
fci_doublet_1 = ActiveSpaceSolver(hf_doublet,
type='FCI',
states=state_doublet_1)
fci_doublet_1.run()
# check results
assert hf_doublet.value('hf energy') == pytest.approx(
ref_hf_energy, 1.0e-10)
assert fci_doublet_1.value(
'active space energy')[state_doublet_1] == pytest.approx(
[ref_fci_energy], 1.0e-10)
# compute the FCI energy for the double B1 (M_S = 1/2) solution
state_doublet_2 = input.state(charge=0, multiplicity=2, ms=-0.5, sym='b1')
fci_doublet_2 = ActiveSpaceSolver(hf_doublet,
type='FCI',
states=state_doublet_2)
fci_doublet_2.run()
assert fci_doublet_2.value(
'active space energy')[state_doublet_2] == pytest.approx(
[ref_fci_energy], 1.0e-10)
state = input.state(charge=1, multiplicity=3, sym='b1')
ref_hf_triplet = -37.066693498042760
ref_fci_triplet = -37.088876452204509
hf_triplet = HF(input, state=state, docc=[2, 0, 0, 0], socc=[1, 0, 1, 0])
hf_triplet.run()
# compute the FCI energy for the triplet B1 (M_S = 1) solution
state_triplet_1 = input.state(charge=1, multiplicity=3, ms=1.0, sym='b1')
fci_triplet_1 = ActiveSpaceSolver(hf_triplet,
type='FCI',
states=state_triplet_1)
fci_triplet_1.run()
# check results
assert hf_triplet.value('hf energy') == pytest.approx(
ref_hf_triplet, 1.0e-10)
assert fci_triplet_1.value(
'active space energy')[state_triplet_1] == pytest.approx(
[ref_fci_triplet], 1.0e-10)
# compute the FCI energy for the triplet B1 (M_S = 0) solution
state_triplet_2 = input.state(charge=1, multiplicity=3, ms=0.0, sym='b1')
fci_triplet_2 = ActiveSpaceSolver(hf_triplet,
type='FCI',
states=state_triplet_2)
fci_triplet_2.run()
assert fci_triplet_2.value(
'active space energy')[state_triplet_2] == pytest.approx(
[ref_fci_triplet], 1.0e-10)
# compute the FCI energy for the triplet B1 (M_S = 0) solution
state_triplet_3 = input.state(charge=1, multiplicity=3, ms=-1.0, sym='b1')
fci_triplet_3 = ActiveSpaceSolver(hf_triplet,
type='FCI',
states=state_triplet_3)
fci_triplet_3.run()
assert fci_triplet_3.value(
'active space energy')[state_triplet_3] == pytest.approx(
[ref_fci_triplet], 1.0e-10)
def test_detci_3():
"""Test DETCI transition dipole and oscillator strengths"""
ref_hf_energy = -154.80914322697598
ref_ag_energies = [
-154.84695193645672, -154.59019912152513, -154.45363253270600
]
ref_bu_energies = [-154.54629332287075]
ref_osc_0ag_0bu = 1.086716030595
ref_osc_1ag_0bu = 0.013542791095
ref_osc_2ag_0bu = 0.041762051475
# setup job
butadiene = """
H 1.080977 -2.558832 0.000000
H -1.080977 2.558832 0.000000
H 2.103773 -1.017723 0.000000
H -2.103773 1.017723 0.000000
H -0.973565 -1.219040 0.000000
H 0.973565 1.219040 0.000000
C 0.000000 0.728881 0.000000
C 0.000000 -0.728881 0.000000
C 1.117962 -1.474815 0.000000
C -1.117962 1.474815 0.000000
"""
input = solver_factory(molecule=butadiene,
basis='def2-svp',
scf_aux_basis='def2-universal-jkfit',
corr_aux_basis='def2-universal-jkfit',
int_type='df')
state = input.state(charge=0, multiplicity=1, sym='ag')
hf = HF(input, state=state, d_convergence=1.0e-12)
hf.run()
assert hf.value('hf energy') == pytest.approx(ref_hf_energy, 1.0e-10)
# define two states with different number of GAS constraints
ag_state = input.state(charge=0, multiplicity=1, sym='ag')
bu_state = input.state(charge=0, multiplicity=1, sym='bu')
# define the active space
mo_spaces = input.mo_spaces(frozen_docc=[2, 0, 0, 2],
restricted_docc=[5, 0, 0, 4],
active=[0, 2, 2, 0])
# create a detci solver
fci = ActiveSpaceSolver(hf,
type='detci',
states={
ag_state: 3,
bu_state: 1
},
mo_spaces=mo_spaces,
options={'transition_dipoles': True})
fci.run()
# check results
assert fci.value('active space energy')[ag_state] == pytest.approx(
ref_ag_energies, 1.0e-10)
assert fci.value('active space energy')[bu_state] == pytest.approx(
ref_bu_energies, 1.0e-10)
print("Oscillator strength singlet 0Ag -> 0Bu")
assert psi4.core.variable("OSC. SINGLET 0AG -> 0BU") == pytest.approx(
ref_osc_0ag_0bu, 1.0e-8)
print("Oscillator strength singlet 1Ag -> 0Bu")
assert psi4.core.variable("OSC. SINGLET 1AG -> 0BU") == pytest.approx(
ref_osc_1ag_0bu, 1.0e-8)
print("Oscillator strength singlet 2Ag -> 0Bu")
assert psi4.core.variable("OSC. SINGLET 2AG -> 0BU") == pytest.approx(
ref_osc_2ag_0bu, 1.0e-8)
