def test_mc1step_9o8e(self):
mc = mcscf.approx_hessian(mcscf.CASSCF(mf, 9, 8))
mc.conv_tol = 1e-8
mo = mf.mo_coeff.copy()
mo[:,[15,16,17,18]] = mf.mo_coeff[:,[17,18,15,16]]
emc = mc.mc1step(mo)[0]
self.assertAlmostEqual(emc, -230.72211519779304, 6)
def test_casci_from_uhf(self):
mf = scf.UHF(mol)
mf.scf()
mc = mcscf.approx_hessian(mcscf.CASSCF(mf, 4, 4))
emc = mc.mc1step()[0]
self.assertAlmostEqual(emc, -108.913786407955, 7)
emc = mc.mc2step()[0]
self.assertAlmostEqual(emc, -108.913786407955, 7)
def test_get_h2eff(self):
mc1 = mcscf.approx_hessian(mcscf.UCASCI(m, 5, (4,2), ncore=(2,2)))
mc1.max_memory = 0
eri1 = mc1.get_h2eff((m.mo_coeff[0][:,2:7], m.mo_coeff[1][:,2:7]))
eri2 = mc1.get_h2cas((m.mo_coeff[0][:,2:7], m.mo_coeff[1][:,2:7]))
self.assertAlmostEqual(abs(eri1[0]-eri2[0]).max(), 0, 12)
self.assertAlmostEqual(abs(eri1[1]-eri2[1]).max(), 0, 12)
self.assertAlmostEqual(abs(eri1[2]-eri2[2]).max(), 0, 12)
def test_get_h2eff(self):
mc1 = mcscf.approx_hessian(mcscf.CASCI(m, 4, 4))
eri1 = mc1.get_h2eff(m.mo_coeff[:,5:9])
eri2 = mc1.get_h2cas(m.mo_coeff[:,5:9])
self.assertAlmostEqual(abs(eri1-eri2).max(), 0, 12)
mc1 = mcscf.density_fit(mcscf.CASCI(m, 4, 4))
eri1 = mc1.get_h2eff(m.mo_coeff[:,5:9])
eri2 = mc1.get_h2cas(m.mo_coeff[:,5:9])
self.assertTrue(abs(eri1-eri2).max() > 1e-5)
mol.spin = 4
mol.symmetry = True
mol.build()
mf = scf.ROHF(mol)
mf = scf.fast_newton(mf)
#
# CAS(16e, 20o)
#
# mcscf.approx_hessian approximates the orbital hessian. It does not affect
# results. The N-2pz orbitals introduces more entanglement to environment.
# 5 bath orbitals which have the strongest entanglement to impurity are
# considered in active space.
#
mc = mcscf.approx_hessian(dmrgscf.dmrgci.DMRGSCF(mf, 20, 16))
idx = [
i for i, s in enumerate(mol.spheric_labels(1))
if 'Fe 3d' in s or 'Fe 4d' in s or 'Fe 4s' in s or 'N 2pz' in s
]
mo = dmet_cas(mc, mf.make_rdm1(), idx)
mc.fcisolver.wfnsym = 'Ag'
mc.kernel(mo)
#mc.analyze()
e_q = mc.e_tot # -2244.90267106288
cas_q = mc.mo_coeff[:, mc.ncore:mc.ncore + mc.ncas]
#
# call DMRG-NEVPT2 (about 2 days, 100 GB memory)
#
def test_mc2step_symm_4o4e(self):
mc = mcscf.approx_hessian(mcscf.CASSCF(msym, 4, 4))
emc = mc.mc2step()[0]
self.assertAlmostEqual(emc, -108.913786407955, 7)
self.assertAlmostEqual(numpy.linalg.norm(mc.analyze()),
2.7015375913946591, 4)
def test_mc2step_symm_6o6e(self):
mc = mcscf.approx_hessian(mcscf.CASSCF(msym, 6, 6))
emc = mc.mc2step()[0]
self.assertAlmostEqual(emc, -108.980105451388, 7)
mol.verbose = 4 mol.output = 'fepor.out' mol.spin = 4 mol.symmetry = True mol.build() mf = scf.ROHF(mol) mf = scf.fast_newton(mf) # ao_labels are keyword(s) to match the AOs generated by mol.ao_labels() # function. ao_labels can be a string, or a pattern of regular expression # or a list of strings/patterns. The code can detect the format and find # the AOs to be taken into the active space. # See also function gto.mole.search_ao_label for the rules of ao_pattern ao_pattern = ['Fe 3d', 'Fe 4d'] ncas, nelecas, mo = dmet_cas.guess_cas(mf, mf.make_rdm1(), ao_pattern) mc = mcscf.approx_hessian(mcscf.CASSCF(mf, ncas, nelecas)) mc.kernel(mo) e_q = mc.e_tot # -2244.82910509839 ################################################## # # Triplet # ##################################################
def test_mc2step_4o4e(self):
mc = mcscf.approx_hessian(mcscf.CASSCF(mf, 4, 4), auxbasis='weigend')
mc.conv_tol = 1e-8
emc = mc.mc2step()[0]
self.assertAlmostEqual(emc, -230.6627383822, 7)
mol.verbose = 4 mol.output = 'fepor.out' mol.spin = 4 mol.symmetry = True mol.build() mf = scf.ROHF(mol) mf = scf.fast_newton(mf) # # CAS(8e, 11o) # # mcscf.approx_hessian approximates the orbital hessian. It does not affect # CASSCF results. # mc = mcscf.approx_hessian(mcscf.CASSCF(mf, 11, 8)) # Function mol.search_ao_label returns the indices of the required AOs # It is equivalent to the following expression #idx = [i for i,s in enumerate(mol.ao_labels()) if 'Fe 3d' in s or 'Fe 4d' in s] idx = mol.search_ao_label(['Fe 3d', 'Fe 4d']) mo = dmet_cas(mc, mf.make_rdm1(), idx) mc.fcisolver.wfnsym = 'Ag' mc.kernel(mo) #mc.analyze() e_q = mc.e_tot # -2244.82910509839 cas_q = mc.mo_coeff[:, mc.ncore:mc.ncore + mc.ncas] ################################################## # # Triplet
def test_mc1step_4o4e(self):
mc = mcscf.approx_hessian(mcscf.CASSCF(mf, 4, 4))
mc.conv_tol = 1e-8
emc = mc.mc1step()[0]
self.assertAlmostEqual(emc, -230.6627383823, 7)
def test_mc1step_4o4e(self):
mc = mcscf.approx_hessian(mcscf.CASSCF(mf, 4, 4))
mc.conv_tol = 1e-8
emc = mc.mc1step()[0]
self.assertAlmostEqual(emc, -230.6627383823, 7)
def test_mc2step_4o4e(self):
mc = mcscf.approx_hessian(mcscf.CASSCF(mf, 4, 4), auxbasis='weigend')
mc.conv_tol = 1e-8
emc = mc.mc2step()[0]
self.assertAlmostEqual(emc, -230.6627383822, 7)
Approximate CASSCF orbital hessian with density fitting integrals
'''
mol = gto.Mole()
mol.build(
atom = [
["C", (-0.65830719, 0.61123287, -0.00800148)],
["C", ( 0.73685281, 0.61123287, -0.00800148)],
["C", ( 1.43439081, 1.81898387, -0.00800148)],
["C", ( 0.73673681, 3.02749287, -0.00920048)],
["C", (-0.65808819, 3.02741487, -0.00967948)],
["C", (-1.35568919, 1.81920887, -0.00868348)],
["H", (-1.20806619, -0.34108413, -0.00755148)],
["H", ( 1.28636081, -0.34128013, -0.00668648)],
["H", ( 2.53407081, 1.81906387, -0.00736748)],
["H", ( 1.28693681, 3.97963587, -0.00925948)],
["H", (-1.20821019, 3.97969587, -0.01063248)],
["H", (-2.45529319, 1.81939187, -0.00886348)],],
basis = 'ccpvtz'
)
mf = scf.RHF(mol)
mf.conv_tol = 1e-8
e = mf.kernel()
mc = mcscf.approx_hessian(mcscf.CASSCF(mf, 6, 6))
mo = mc.sort_mo([17,20,21,22,23,30])
mc.kernel(mo)
print('E(CAS) = %.12f, ref = -230.848493421389' % mc.e_tot)
mol.spin = 4 mol.symmetry = True mol.build() mf = scf.ROHF(mol) mf = scf.fast_newton(mf) # # CAS(16e, 20o) # # mcscf.approx_hessian approximates the orbital hessian. It does not affect # results. The N-2pz orbitals introduces more entanglement to environment. # 5 bath orbitals which have the strongest entanglement to impurity are # considered in active space. # mc = mcscf.approx_hessian(dmrgscf.dmrgci.DMRGSCF(mf, 20, 16)) # Function mol.search_ao_label returns the indices of the required AOs # It is equivalent to the following expression #idx = [i for i,s in enumerate(mol.ao_labels()) # if 'Fe 3d' in s or 'Fe 4d' in s or 'Fe 4s' in s or 'N 2pz' in s] idx = mol.search_ao_label(['Fe 3d', 'Fe 4d', 'Fe 4s', 'N 2pz']) mo = dmet_cas(mc, mf.make_rdm1(), idx) mc.fcisolver.wfnsym = 'Ag' mc.kernel(mo) #mc.analyze() e_q = mc.e_tot # -2244.90267106288 cas_q = mc.mo_coeff[:,mc.ncore:mc.ncore+mc.ncas] # # call DMRG-NEVPT2 (about 2 days, 100 GB memory)
mol.verbose = 4 mol.output = 'fepor.out' mol.spin = 4 mol.symmetry = True mol.build() mf = scf.ROHF(mol) mf = scf.fast_newton(mf) # # CAS(8e, 11o) # # mcscf.approx_hessian approximates the orbital hessian. It does not affect # CASSCF results. # mc = mcscf.approx_hessian(mcscf.CASSCF(mf, 11, 8)) # Function mol.search_ao_label returns the indices of the required AOs # It is equivalent to the following expression #idx = [i for i,s in enumerate(mol.ao_labels()) if 'Fe 3d' in s or 'Fe 4d' in s] idx = mol.search_ao_label(['Fe 3d', 'Fe 4d']) mo = dmet_cas(mc, mf.make_rdm1(), idx) mc.fcisolver.wfnsym = 'Ag' mc.kernel(mo) #mc.analyze() e_q = mc.e_tot # -2244.82910509839 cas_q = mc.mo_coeff[:,mc.ncore:mc.ncore+mc.ncas]
def test_mc1step_symm_4o4e(self):
mc = mcscf.approx_hessian(mcscf.CASSCF(msym, 4, 4), auxbasis='weigend')
emc = mc.mc1step()[0]
self.assertAlmostEqual(emc, -108.913786407955, 7)
self.assertAlmostEqual(numpy.linalg.norm(mc.analyze()),
2.7015375913946591, 4)
def test_mc2step_6o6e_high_cost(self):
mc = mcscf.approx_hessian(mcscf.CASSCF(m, 6, 6), auxbasis='weigend')
emc = mc.mc2step()[0]
self.assertAlmostEqual(emc, -108.980105451388, 7)
def test_mc2step_symm_6o6e(self):
mc = mcscf.approx_hessian(mcscf.CASSCF(msym, 6, 6))
emc = mc.mc2step()[0]
self.assertAlmostEqual(emc, -108.980105451388, 7)
def test_mc2step_6o6e_high_cost(self):
mc = mcscf.approx_hessian(mcscf.CASSCF(m, 6, 6), auxbasis='weigend')
emc = mc.mc2step()[0]
self.assertAlmostEqual(emc, -108.980105451388, 7)
