def test_ccsd_grad(self):
mycc = cc.ccsd.CCSD(mf)
mycc.max_memory = 1
mycc.conv_tol = 1e-10
eris = mycc.ao2mo()
ecc, t1, t2 = mycc.kernel(eris=eris)
l1, l2 = mycc.solve_lambda(eris=eris)
g1 = ccsd_grad.kernel(mycc, t1, t2, l1, l2, mf_grad=grad.RHF(mf))
self.assertAlmostEqual(lib.finger(g1), -0.036999389889460096, 6)
mol = gto.M(
verbose = 5,
output = '/dev/null',
atom = 'H 0 0 0; H 0 0 1.706',
basis = '631g',
unit='Bohr')
mf0 = scf.RHF(mol).run(conv_tol=1e-14)
mycc0 = cc.ccsd.CCSD(mf0).run(conv_tol=1e-10)
mol.set_geom_('H 0 0 0; H 0 0 1.704', unit='Bohr')
mf1 = scf.RHF(mol).run(conv_tol=1e-14)
mycc1= cc.ccsd.CCSD(mf1).run(conv_tol=1e-10)
mol.set_geom_('H 0 0 0; H 0 0 1.705', unit='Bohr')
mycc2 = cc.ccsd.CCSD(scf.RHF(mol))
g_scanner = mycc2.nuc_grad_method().as_scanner().as_scanner()
g1 = g_scanner(mol)[1]
self.assertTrue(g_scanner.converged)
self.assertAlmostEqual(g1[0,2], (mycc1.e_tot-mycc0.e_tot)*500, 6)
def test_ccsd_grad(self):
mycc = cc.ccsd.CCSD(mf)
mycc.max_memory = 1
mycc.conv_tol = 1e-10
eris = mycc.ao2mo()
ecc, t1, t2 = mycc.kernel(eris=eris)
l1, l2 = mycc.solve_lambda(eris=eris)
g1 = ccsd_grad.kernel(mycc, t1, t2, l1, l2, mf_grad=grad.RHF(mf))
self.assertAlmostEqual(lib.finger(g1), -0.036999389889460096, 6)
mol = gto.M(
verbose = 5,
output = '/dev/null',
atom = 'H 0 0 0; H 0 0 1.706',
basis = '631g',
unit='Bohr')
mf0 = scf.RHF(mol).run(conv_tol=1e-14)
mycc0 = cc.ccsd.CCSD(mf0).run(conv_tol=1e-10)
mol.set_geom_('H 0 0 0; H 0 0 1.704', unit='Bohr')
mf1 = scf.RHF(mol).run(conv_tol=1e-14)
mycc1= cc.ccsd.CCSD(mf1).run(conv_tol=1e-10)
mol.set_geom_('H 0 0 0; H 0 0 1.705', unit='Bohr')
mycc2 = cc.ccsd.CCSD(scf.RHF(mol))
g_scanner = mycc2.nuc_grad_method().as_scanner().as_scanner()
g1 = g_scanner(mol)[1]
self.assertTrue(g_scanner.converged)
self.assertAlmostEqual(g1[0,2], (mycc1.e_tot-mycc0.e_tot)*500, 6)
def kernel(mycc,
t1=None,
t2=None,
l1=None,
l2=None,
eris=None,
atmlst=None,
mf_grad=None,
verbose=lib.logger.INFO):
if t1 is None: t1 = mycc.t1
if t2 is None: t2 = mycc.t2
if l1 is None: l1 = mycc.l1
if l2 is None: l2 = mycc.l2
d1 = ccsd_t_rdm._gamma1_intermediates(mycc,
t1,
t2,
l1,
l2,
eris,
for_grad=True)
fd2intermediate = lib.H5TmpFile()
d2 = ccsd_t_rdm._gamma2_outcore(mycc, t1, t2, l1, l2, eris,
fd2intermediate, True)
return ccsd_grad.kernel(mycc, t1, t2, l1, l2, eris, atmlst, mf_grad, d1,
d2, verbose)
def casci_grad_with_ccsd_solver(mc,
mo_coeff=None,
ci=None,
atmlst=None,
mf_grad=None,
verbose=None):
if mo_coeff is None: mo_coeff = mc._scf.mo_coeff
if ci is None: ci = mc.ci
if mf_grad is None: mf_grad = mc._scf.nuc_grad_method()
mol = mc.mol
ncore = mc.ncore
ncas = mc.ncas
nocc = ncore + ncas
nelecas = mc.nelecas
nao, nmo = mo_coeff.shape
nao_pair = nao * (nao + 1) // 2
mo_occ = mo_coeff[:, :nocc]
mo_core = mo_coeff[:, :ncore]
mo_cas = mo_coeff[:, ncore:nocc]
casdm1, casdm2 = mc.fcisolver.make_rdm12(mc.ci, ncas, nelecas)
no = mc.nelecas[0]
for i in range(no):
casdm1[i, i] -= 2
for i in range(no):
for j in range(no):
casdm2[i, i, j, j] -= 4
casdm2[i, j, j, i] += 2
for i in range(no):
casdm2[i, i, :, :] -= casdm1 * 2
casdm2[:, :, i, i] -= casdm1 * 2
casdm2[:, i, i, :] += casdm1
casdm2[i, :, :, i] += casdm1
mc.mo_occ = mc._scf.mo_occ
mask = numpy.zeros(nmo, dtype=bool)
mask[ncore:nocc] = True
mc.frozen = numpy.where(~mask)[0]
mc.get_frozen_mask = lambda *args: mask
d1 = (casdm1[:no, :no] * .5, casdm1[:no, no:] * .5, casdm1[no:, :no] * .5,
casdm1[no:, no:] * .5)
casdm2 = (casdm2 + casdm2.transpose(1, 0, 2, 3)) * .5
vvvv = casdm2[no:, no:, no:, no:]
d2 = (casdm2[:no, no:, :no, no:] * .5, ao2mo.restore(4, vvvv, ncas - no) *
.25, casdm2[:no, :no, :no, :no] * .25,
casdm2[:no, :no, no:, no:] * .5, casdm2[:no, no:, no:, :no] * .5,
casdm2, casdm2[:no, no:, no:, no:], casdm2[:no, :no, :no, no:])
mc.mo_coeff = mo_coeff
t1 = t2 = l1 = l2 = ci
return ccsd_grad.kernel(mc, t1, t2, l1, l2, None, atmlst, mf_grad, d1, d2,
verbose)
def kernel(myci, civec=None, eris=None, atmlst=None, mf_grad=None,
verbose=logger.INFO):
if civec is None: civec = myci.ci
assert(not isinstance(civec, (list, tuple)))
nocc = myci.nocc
nmo = myci.nmo
d1 = cisd._gamma1_intermediates(myci, civec, nmo, nocc)
fd2intermediate = lib.H5TmpFile()
d2 = cisd._gamma2_outcore(myci, civec, nmo, nocc, fd2intermediate, True)
t1 = t2 = l1 = l2 = civec
return ccsd_grad.kernel(myci, t1, t2, l1, l2, eris, atmlst, mf_grad,
d1, d2, verbose)
def casci_grad_with_ccsd_solver(mc, mo_coeff=None, ci=None, atmlst=None, mf_grad=None,
verbose=None):
if mo_coeff is None: mo_coeff = mc._scf.mo_coeff
if ci is None: ci = mc.ci
if mf_grad is None: mf_grad = mc._scf.nuc_grad_method()
mol = mc.mol
ncore = mc.ncore
ncas = mc.ncas
nocc = ncore + ncas
nelecas = mc.nelecas
nao, nmo = mo_coeff.shape
nao_pair = nao * (nao+1) // 2
mo_occ = mo_coeff[:,:nocc]
mo_core = mo_coeff[:,:ncore]
mo_cas = mo_coeff[:,ncore:nocc]
casdm1, casdm2 = mc.fcisolver.make_rdm12(mc.ci, ncas, nelecas)
no = mc.nelecas[0]
for i in range(no):
casdm1[i,i] -= 2
for i in range(no):
for j in range(no):
casdm2[i,i,j,j] -= 4
casdm2[i,j,j,i] += 2
for i in range(no):
casdm2[i,i,:,:] -= casdm1 * 2
casdm2[:,:,i,i] -= casdm1 * 2
casdm2[:,i,i,:] += casdm1
casdm2[i,:,:,i] += casdm1
mc.mo_occ = mc._scf.mo_occ
mask = numpy.zeros(nmo, dtype=bool)
mask[ncore:nocc] = True
mc.frozen = numpy.where(~mask)[0]
mc.get_frozen_mask = lambda *args: mask
d1 = (casdm1[:no,:no] * .5, casdm1[:no,no:] * .5,
casdm1[no:,:no] * .5, casdm1[no:,no:] * .5)
casdm2 = (casdm2 + casdm2.transpose(1,0,2,3)) * .5
vvvv = casdm2[no:,no:,no:,no:]
d2 = (casdm2[:no,no:,:no,no:] * .5,
ao2mo.restore(4, vvvv, ncas-no) * .25,
casdm2[:no,:no,:no,:no] * .25,
casdm2[:no,:no,no:,no:] * .5,
casdm2[:no,no:,no:,:no] * .5, casdm2,
casdm2[:no,no:,no:,no:],
casdm2[:no,:no,:no,no:])
mc.mo_coeff = mo_coeff
t1 = t2 = l1 = l2 = ci
return ccsd_grad.kernel(mc, t1, t2, l1, l2, None, atmlst, mf_grad,
d1, d2, verbose)
def kernel(mycc, t1=None, t2=None, l1=None, l2=None, eris=None, atmlst=None,
mf_grad=None, verbose=lib.logger.INFO):
if t1 is None: t1 = mycc.t1
if t2 is None: t2 = mycc.t2
if l1 is None: l1 = mycc.l1
if l2 is None: l2 = mycc.l2
d1 = ccsd_t_rdm._gamma1_intermediates(mycc, t1, t2, l1, l2, eris,
for_grad=True)
fd2intermediate = lib.H5TmpFile()
d2 = ccsd_t_rdm._gamma2_outcore(mycc, t1, t2, l1, l2, eris,
fd2intermediate, True)
return ccsd_grad.kernel(mycc, t1, t2, l1, l2, eris, atmlst, mf_grad,
d1, d2, verbose)