def test_scf_grad(self):
mf = ddcosmo.ddcosmo_for_scf(scf.RHF(mol0)).run()
# solvent only
de_cosmo = ddcosmo_grad.kernel(mf.with_solvent, mf.make_rdm1())
self.assertAlmostEqual(lib.fp(de_cosmo), 0.000770107393352652, 6)
# solvent + solute
de = mf.nuc_grad_method().kernel()
self.assertAlmostEqual(lib.fp(de), -0.1920179073822721, 6)
dm1 = mf.make_rdm1()
mf1 = ddcosmo.ddcosmo_for_scf(scf.RHF(mol1)).run()
e1 = mf1.e_tot
e1_cosmo = mf1.with_solvent.energy(dm1)
mf2 = ddcosmo.ddcosmo_for_scf(scf.RHF(mol2)).run()
e2 = mf2.e_tot
e2_cosmo = mf2.with_solvent.energy(dm1)
self.assertAlmostEqual(abs((e2 - e1) / dx - de[0, 2]).max(), 0, 7)
self.assertAlmostEqual(
abs((e2_cosmo - e1_cosmo) / dx - de_cosmo[0, 2]).max(), 0, 7)
sc = mf.nuc_grad_method().as_scanner()
e, g = sc('H 0 1 0; H 0 1 1.2; H 1. 0 0; H .5 .5 0')
self.assertAlmostEqual(e, -0.8317337703056022, 8)
self.assertAlmostEqual(lib.fp(g), 0.06804297145388238, 6)
mol3 = gto.M(atom='H 0 1 0; H 0 1 1.2; H 1. 0 0; H .5 .5 0', unit='B')
mf = ddcosmo.ddcosmo_for_scf(scf.RHF(mol3)).run()
de = mf.nuc_grad_method().kernel()
self.assertAlmostEqual(lib.fp(de), 0.06804297145388238, 6)
def test_e_cosmo_grad(self):
pcmobj = ddcosmo.DDCOSMO(mol0)
de = ddcosmo_grad.kernel(pcmobj, dm)
pcmobj = ddcosmo.DDCOSMO(mol1)
e1 = pcmobj.energy(dm)
pcmobj = ddcosmo.DDCOSMO(mol2)
e2 = pcmobj.energy(dm)
self.assertAlmostEqual(abs((e2 - e1) / dx - de[0, 2]).max(), 0, 7)
def test_e_cosmo_grad(self):
pcmobj = ddcosmo.DDCOSMO(mol0)
de = ddcosmo_grad.kernel(pcmobj, dm)
pcmobj = ddcosmo.DDCOSMO(mol1)
e1 = pcmobj.energy(dm)
pcmobj = ddcosmo.DDCOSMO(mol2)
e2 = pcmobj.energy(dm)
self.assertAlmostEqual(abs((e2-e1)/dx - de[0,2]).max(), 0, 7)
def test_scf_grad(self):
mf = ddcosmo.ddcosmo_for_scf(scf.RHF(mol0)).run()
de_cosmo = ddcosmo_grad.kernel(mf._solvent, mf.make_rdm1())
de = mf.nuc_grad_method().kernel()
dm1 = mf.make_rdm1()
mf = ddcosmo.ddcosmo_for_scf(scf.RHF(mol1)).run()
e1 = mf.e_tot
e1_cosmo = mf._solvent.energy(dm1)
mf = ddcosmo.ddcosmo_for_scf(scf.RHF(mol2)).run()
e2 = mf.e_tot
e2_cosmo = mf._solvent.energy(dm1)
self.assertAlmostEqual(abs((e2-e1)/dx - de[0,2]).max(), 0, 7)
self.assertAlmostEqual(abs((e2_cosmo-e1_cosmo)/dx - de_cosmo[0,2]).max(), 0, 7)
def test_scf_grad(self):
mf = ddcosmo.ddcosmo_for_scf(scf.RHF(mol0)).run()
de_cosmo = ddcosmo_grad.kernel(mf.with_solvent, mf.make_rdm1())
de = mf.nuc_grad_method().kernel()
dm1 = mf.make_rdm1()
mf = ddcosmo.ddcosmo_for_scf(scf.RHF(mol1)).run()
e1 = mf.e_tot
e1_cosmo = mf.with_solvent.energy(dm1)
mf = ddcosmo.ddcosmo_for_scf(scf.RHF(mol2)).run()
e2 = mf.e_tot
e2_cosmo = mf.with_solvent.energy(dm1)
self.assertAlmostEqual(abs((e2-e1)/dx - de[0,2]).max(), 0, 7)
self.assertAlmostEqual(abs((e2_cosmo-e1_cosmo)/dx - de_cosmo[0,2]).max(), 0, 7)
def test_B1(self):
def getB(mol):
pcm = ddcosmo.DDCOSMO(mol)
pcm.lmax = 2
pcm.eps = 0
natm = mol.natm
nao = mol.nao
nlm = (pcm.lmax + 1)**2
r_vdw = ddcosmo.get_atomic_radii(pcm)
fi = ddcosmo.make_fi(pcm, r_vdw)
ui = 1 - fi
ui[ui < 0] = 0
pcm.grids = grids = dft.gen_grid.Grids(mol).run(level=0)
coords_1sph, weights_1sph = ddcosmo.make_grids_one_sphere(
pcm.lebedev_order)
ylm_1sph = numpy.vstack(
sph.real_sph_vec(coords_1sph, pcm.lmax, True))
cached_pol = ddcosmo.cache_fake_multipoles(grids, r_vdw, pcm.lmax)
L = ddcosmo.make_L(pcm, r_vdw, ylm_1sph, fi)
return make_B(pcm, r_vdw, ui, ylm_1sph, cached_pol, L)
pcm = ddcosmo.DDCOSMO(mol0)
pcm.lmax = 2
pcm.eps = 0
natm = mol0.natm
nao = mol0.nao
nlm = (pcm.lmax + 1)**2
r_vdw = ddcosmo.get_atomic_radii(pcm)
fi = ddcosmo.make_fi(pcm, r_vdw)
ui = 1 - fi
ui[ui < 0] = 0
pcm.grids = grids = dft.gen_grid.Grids(mol0).run(level=0)
coords_1sph, weights_1sph = ddcosmo.make_grids_one_sphere(
pcm.lebedev_order)
ylm_1sph = numpy.vstack(sph.real_sph_vec(coords_1sph, pcm.lmax, True))
cached_pol = ddcosmo.cache_fake_multipoles(grids, r_vdw, pcm.lmax)
L = ddcosmo.make_L(pcm, r_vdw, ylm_1sph, fi)
dB = make_B1(pcm, r_vdw, ui, ylm_1sph, cached_pol, L)
B1 = getB(mol1)
B2 = getB(mol2)
self.assertAlmostEqual(abs((B2 - B1) / dx - dB[0, 2]).max(), 0, 8)
nao = mol0.nao
numpy.random.seed(1)
dm1 = numpy.random.random((2, nao, nao))
dm2 = numpy.random.random((2, nao, nao))
dm = dm1[0]
ref = numpy.einsum('azpqrs,npq->nazrs', dB, dm1)
v = B1_dot_x(pcm, dm, r_vdw, ui, ylm_1sph, cached_pol, L)
self.assertAlmostEqual(abs(v - ref[0]).max(), 0, 12)
de = _ddcosmo_tdscf_grad._grad_ee(pcm, dm1, dm2, r_vdw, ui, ylm_1sph,
cached_pol, L)
ref = numpy.einsum('nazij,nij->naz', ref, dm2)
self.assertAlmostEqual(abs(de - ref).max(), 0, 12)
numpy.random.seed(1)
dm = numpy.random.random((nao, nao))
dm = dm + dm.T
ref = ddcosmo_grad.kernel(pcm, dm)
dielectric = pcm.eps
if dielectric > 0:
f_epsilon = (dielectric - 1.) / dielectric
else:
f_epsilon = 1
de = _ddcosmo_tdscf_grad._grad_nn(pcm, r_vdw, ui, ylm_1sph, cached_pol,
L)
de += _ddcosmo_tdscf_grad._grad_ne(pcm, dm, r_vdw, ui, ylm_1sph,
cached_pol, L)
de += .5 * _ddcosmo_tdscf_grad._grad_ee(pcm, dm, dm, r_vdw, ui,
ylm_1sph, cached_pol, L)
de *= .5 * f_epsilon
self.assertAlmostEqual(abs(de - ref).max(), 0, 12)