def test_energy1(self):
mol = gto.M(
verbose = 0,
atom = '''
O 0 0 0
O 0 0 1.207''',
basis = '6-31g',
spin = 2)
m = scf.RHF(mol)
m.scf()
mc = mcscf.CASCI(m, 6, 8)
mc.fcisolver.conv_tol = 1e-16
mc.kernel()
e = nevpt2.sc_nevpt(mc)
self.assertAlmostEqual(e, -0.16978532268234559, 6)
mc.chkfile = 'hs_mc.chk'
mo = scf.chkfile.load('hs_mc.chk', "mcscf/mo_coeff")
mc.fcisolver = DMRGCI(mol,maxM=500, tol =1e-8)
#
# Tune DMRG parameters. It's not necessary in most scenario.
#
#mc.fcisolver.outputlevel = 3
#mc.fcisolver.scheduleSweeps = [0, 4, 8, 12, 16, 20, 24, 28, 30, 34]
#mc.fcisolver.scheduleMaxMs = [200, 400, 800, 1200, 2000, 4000, 3000, 2000, 1000, 500]
#mc.fcisolver.scheduleTols = [0.0001, 0.0001, 0.0001, 0.0001, 1e-5, 1e-6, 1e-7, 1e-7, 1e-7, 1e-7 ]
#mc.fcisolver.scheduleNoises = [0.0001, 0.0001, 0.0001, 0.0001, 0.0001, 0.0001, 0.0, 0.0, 0.0, 0.0]
#mc.fcisolver.twodot_to_onedot = 38
#mc.fcisolver.maxIter = 50
mc.casci(mo)
#
# DMRG-NEVPT2
#
# There is a fast DMRG-NEVPT2 implementation. See also the example
# pyscf/examples/dmrg/02-dmrg_nevpt2.py
#
sc_nevpt(mc)
##################################################
#
# Don't forget to clean up the scratch. DMRG calculation can produce large
# amount of temporary files.
#
##################################################
sol = COSMO(mol)
sol.eps = -1
mf = cosmo_for_scf(scf.RHF(mol), sol)
mf.init_guess = 'atom' # otherwise it cannot converge to the correct result!
escf = mf.kernel()
sol.eps = 37
mc = mcscf.CASSCF(mf, 4, 4)
mc = cosmo_for_mcscf(mc, sol)
mo = mc.sort_mo([3,4,6,7])
emc = mc.kernel(mo)[0]
assert(abs(emc+75.6377646267)<1.e-6)
mc = mcscf.CASCI(mf, 4, 4)
mc = cosmo_for_casci(mc, sol)
eci = mc.kernel()[0]
assert(abs(eci+75.5789635682)<1.e-6)
# Single-step CASCI
sol.dm = sol._dm_guess
#sol.casci_max_cycle = 1
mc = mcscf.CASCI(mf, 4, 4)
mc = cosmo_for_casci(mc, sol)
eci = mc.kernel()[0]
assert(abs(eci+75.5789635647)<1.e-6)
from pyscf.mrpt.nevpt2 import sc_nevpt
ec = sc_nevpt(mc)
assert(abs(ec+0.128805510364)<1.e-6)
def test_energy(self):
e = nevpt2.sc_nevpt(mc)
self.assertAlmostEqual(e, -0.10315217594326213, 7)
output="out-casscf",
atom=[["H", (0.0, 0.0, i - 3.5)] for i in range(8)],
basis={"H": "sto-3g"},
symmetry="d2h",
)
m = scf.RHF(mol)
m.scf()
mc = mcscf.CASCI(m, 4, 4)
mc.fcisolver.nroots = 2
mc.casci()
file = open("MO", "w")
pickle.dump(mc.mo_coeff, file)
file.close()
ci_nevpt_e1 = sc_nevpt(mc, ci=mc.ci[0])
ci_nevpt_e2 = sc_nevpt(mc, ci=mc.ci[1])
b = 1.4
mol = gto.Mole()
mol.build(
verbose=7,
output="out-dmrg",
atom=[["H", (0.0, 0.0, i - 3.5)] for i in range(8)],
basis={"H": "sto-3g"},
symmetry="d2h",
)
m = scf.RHF(mol)
m.scf()
file = open("MO", "r")
#
# 2. Frozen solvation of ground state for excited states
#
# Assigning certain density matrix to sol.dm can force the solvent object to
# compute the solvation correction with the given density matrix.
# sol._dm_guess is the system density matrix of the last iteration from
# previous calculation. Setting "sol.dm = sol._dm_guess" freezes the
# ground state solvent effects in the excitated calculation.
#
sol.dm = sol._dm_guess
mc = cosmo.cosmo_(mcscf.CASCI(mf, 5, 6), sol)
mc.fcisolver.nroots = 2
mc.kernel(mo)
e_state0 = mc.e_tot[0] + sc_nevpt(mc, ci=mc.ci[0])
e_state1 = mc.e_tot[1] + sc_nevpt(mc, ci=mc.ci[1])
print('Excitation E = %.9g' % (e_state1-e_state0))
##################################################
#
# Emission
#
##################################################
#
# 1. Equilibrium solvation for excited state.
#
# "sol.dm = None" relaxes the solvent to equilibruim wrt excited state
mc = dmrgscf.dmrgci.DMRGSCF(m, 8, 8)
mc.state_average_([.5,.5])
e_0 = mc.kernel()[0]
#
# Run DMRGCI for 2 excited states
#
mc = mcscf.CASCI(m, 8, 8)
mc.fcisolver = dmrgscf.drmgci.DMRGCI(mol, maxM=200)
mc.fcisolver.nroots = 2
e_0 = mc.kernel()[0]
#
# Computing NEVPT2 based on state-specific DMRG-CASCI calculation
#
dmrg_nevpt_e1 = sc_nevpt(mc, ci=mc.ci[0])
dmrg_nevpt_e2 = sc_nevpt(mc, ci=mc.ci[1])
print('DE = %.9g' % (e_0[1]+dmrg_nevpt_e2) - (e_0[0]+dmrg_nevpt_e1))
##################################################
#
# State-specific
#
##################################################
#
# Optimize orbitals for first excited state
#
mc = dmrgscf.dmrgci.DMRGSCF(m, 8, 8)
sol = COSMO(mol)
sol.eps = -1
mf = cosmo_for_scf(scf.RHF(mol), sol)
mf.init_guess = 'atom' # otherwise it cannot converge to the correct result!
escf = mf.kernel()
sol.eps = 37
mc = mcscf.CASSCF(mf, 4, 4)
mc = cosmo_for_mcscf(mc, sol)
mo = mc.sort_mo([3,4,6,7])
emc = mc.kernel(mo)[0]
assert(abs(emc+75.6377646267)<1.e-6)
mc = mcscf.CASCI(mf, 4, 4)
mc = cosmo_for_casci(mc, sol)
eci = mc.kernel()[0]
assert(abs(eci+75.5789635682)<1.e-6)
# Single-step CASCI
sol.dm = sol._dm_guess
#sol.casci_max_cycle = 1
mc = mcscf.CASCI(mf, 4, 4)
mc = cosmo_for_casci(mc, sol)
eci = mc.kernel()[0]
assert(abs(eci+75.5789635647)<1.e-6)
from pyscf.mrpt.nevpt2 import sc_nevpt
ec = sc_nevpt(mc)
assert(abs(ec+0.128805510364)<1.e-6)