def test_HF_B3LYP_hess(self):
from pkg_resources import resource_filename
from pyxdh.Utilities.test_molecules import Mol_H2O2
from pyxdh.DerivOnce import GradNCDFT
import pickle
H2O2 = Mol_H2O2()
config = {
"scf_eng": H2O2.hf_eng,
"nc_eng": H2O2.gga_eng,
"rotation": True,
}
grad_helper = GradNCDFT(config)
config = {
"deriv_A": grad_helper,
"deriv_B": grad_helper,
}
helper = HessNCDFT(config)
E_2 = helper.E_2
with open(resource_filename("pyxdh", "Validation/numerical_deriv/ncdft_hessian_hf_b3lyp.dat"), "rb") as f:
ref_hess = pickle.load(f)["hess"]
assert (np.allclose(
E_2, ref_hess,
atol=1e-6, rtol=1e-4
))
def test_r_hfb3lyp_grad(self):
scf_eng = scf.RHF(self.mol).run()
nc_eng = dft.RKS(self.mol, xc="B3LYPg")
nc_eng.grids = self.grids
gradh = GradNCDFT({"scf_eng": scf_eng, "nc_eng": nc_eng})
with open(resource_filename("pyxdh", "Validation/numerical_deriv/NH3-HFB3LYP-grad.dat"), "rb") as f:
ref_grad = pickle.load(f).reshape(-1, 3)
# ASSERT: energy - theoretical
assert np.allclose(gradh.eng, nc_eng.energy_tot(dm=scf_eng.make_rdm1()))
# ASSERT: grad - numerical
assert np.allclose(gradh.E_1, ref_grad, atol=1e-6, rtol=1e-4)
def mol_to_grad(mol):
grids = dft.Grids(mol)
grids.atom_grid = (99, 590)
grids.build()
scf_eng = scf.RHF(mol)
scf_eng.conv_tol = 1e-12
scf_eng.conv_tol_grad = 1e-10
scf_eng.max_cycle = 256
scf_eng.run()
nc_eng = dft.RKS(mol, xc="B3LYPg")
nc_eng.grids = grids
gradh = GradNCDFT({"scf_eng": scf_eng, "nc_eng": nc_eng})
return gradh.E_1
def dipole_generator(component, interval):
H2O2 = Mol_H2O2()
mol = H2O2.mol
def get_hcore(mol=mol):
return scf.rhf.get_hcore(
mol) - interval * mol.intor("int1e_r")[component]
H2O2.hf_eng.get_hcore = get_hcore
H2O2.gga_eng.get_hcore = get_hcore
config = {"scf_eng": H2O2.hf_eng, "nc_eng": H2O2.gga_eng}
helper = GradNCDFT(config)
return helper
def test_r_hfb3lyp_hess(self):
scf_eng = scf.RHF(self.mol)
scf_eng.conv_tol_grad = 1e-10
scf_eng.max_cycle = 256
scf_eng.run()
nc_eng = dft.RKS(self.mol, xc="B3LYPg")
nc_eng.grids = self.grids
gradh = GradNCDFT({"scf_eng": scf_eng, "nc_eng": nc_eng})
hessh = HessNCDFT({"deriv_A": gradh})
with open(
resource_filename(
"pyxdh",
"Validation/numerical_deriv/NH3-HFB3LYP-hess.dat"),
"rb") as f:
ref_hess = pickle.load(f)
# ASSERT: hessian - numerical
assert np.allclose(hessh.E_2,
ref_hess.reshape((-1, self.mol.natm * 3)),
atol=5e-6,
rtol=1e-4)
def test_HF_B3LYP_dipderiv(self):
from pkg_resources import resource_filename
from pyxdh.Utilities.test_molecules import Mol_H2O2
from pyxdh.DerivOnce import DipoleNCDFT, GradNCDFT
import pickle
H2O2 = Mol_H2O2()
config = {"scf_eng": H2O2.hf_eng, "nc_eng": H2O2.gga_eng}
dip_helper = DipoleNCDFT(config)
grad_helper = GradNCDFT(config)
config = {"deriv_A": dip_helper, "deriv_B": grad_helper}
helper = DipDerivNCDFT(config)
E_2 = helper.E_2
with open(
resource_filename(
"pyxdh",
"Validation/numerical_deriv/ncdft_dipderiv_hf_b3lyp.dat"),
"rb") as f:
ref_dipderiv = pickle.load(f)["dipderiv"]
assert (np.allclose(E_2.T, ref_dipderiv, atol=1e-6, rtol=1e-4))
def mol_to_grad_helper(mol):
H2O2 = Mol_H2O2(mol=mol)
H2O2.hf_eng.kernel()
config = {"scf_eng": H2O2.hf_eng, "nc_eng": H2O2.gga_eng}
helper = GradNCDFT(config)
return helper