def ic3epa(self, **kwargs):
b = self.cepa_b()
b = at.collapse_tensor(b, self)
b = at.concatenate_amps(b, self)
oldguess = np.zeros(len(b))
norm = 1
self.x = 0*b
while abs(norm) > 1e-14:
Aop = scipy.sparse.linalg.LinearOperator((len(b), len(b)), matvec = self.ic3epa_A, rmatvec = self.ic3epa_A)
x, info = np.array(scipy.sparse.linalg.cg(Aop, -b, x0 = self.x, tol = self.tol))
norm = (oldguess - x).dot(oldguess - x)
oldguess = copy.copy(x)
self.lam = .5*x.T.dot(x)
self.x = copy.copy(x)
if self.reference == 'rhf':
#Ax = at.rhf_to_uhf(self.c3epa_A(x), self)
#b = at.rhf_to_uhf(b, self)
#x = at.rhf_to_uhf(x, self)
energy = self.c3epa_energy(x)
else:
#energy = self.hf_energy + 2*x.T.dot(b) + x.T.dot(self.c3epa_A(x))
energy = self.c3epa_energy(x)
return energy
def ic3epa_A(self, x):
term1 = self.cepa_A(x)
term3 = self.x.T.dot(self.A2(self.x))*x
if self.reference == 'rhf':
x = at.rhf_to_uhf(x, self)
x = at.decatenate_amps(x, self, reference = 'uhf')
x = at.expand_vector(x, self, reference = 'uhf')
#Initialize Hessian Shapes
Ax = {}
Ax['a'] = np.zeros((self.noa, self.nva))
Ax['b'] = np.zeros((self.nob, self.nvb))
Ax['aa'] = np.zeros((self.noa, self.noa, self.nva, self.nva))
Ax['ab'] = np.zeros((self.noa, self.nob, self.nva, self.nvb))
Ax['bb'] = np.zeros((self.nob, self.nob, self.nvb, self.nvb))
if self.reference != 'rhf':
Ax['a'] += contract('ijab,jb->ia', self.l_aaaa[:self.noa, :self.noa, self.noa:, self.noa:], x['a'])
Ax['a'] += contract('ijab,jb->ia', self.j_abab[:self.noa, :self.nob, self.noa:, self.nob:], x['b'])
Ax['b'] += contract('ijab,jb->ia', self.l_bbbb[:self.nob, :self.nob, self.nob:, self.nob:], x['b'])
Ax['b'] += contract('jiba,jb->ia', self.j_abab[:self.noa, :self.nob, self.noa:, self.nob:], x['a'])
else:
Ax['a'] += .5*contract('ijab,jb->ia', self.l_aaaa[:self.noa, :self.noa, self.noa:, self.noa:], x['a'])
Ax['a'] += .5*contract('ijab,jb->ia', self.j_abab[:self.noa, :self.nob, self.noa:, self.nob:], x['b'])
Ax['a'] += .5*contract('ijab,jb->ia', self.l_bbbb[:self.nob, :self.nob, self.nob:, self.nob:], x['b'])
Ax['a'] += .5*contract('jiba,jb->ia', self.j_abab[:self.noa, :self.nob, self.noa:, self.nob:], x['a'])
Ax = at.collapse_tensor(Ax, self)
Ax = at.concatenate_amps(Ax, self)
return term1+term3+self.x.dot(self.x)*Ax
def cepa(self):
b = self.cepa_b()
b = at.collapse_tensor(b, self)
b = at.concatenate_amps(b, self)
Aop = scipy.sparse.linalg.LinearOperator((len(b), len(b)), matvec = self.cepa_A, rmatvec = self.cepa_A)
if self.run_svd == True:
#print(scipy.sparse.linalg.eigsh(Aop, k = 3)[0])
print('Getting SVD of H_N:')
print(scipy.sparse.linalg.svds(Aop, k = 3, which = 'SM')[1])
print(scipy.sparse.linalg.svds(Aop, k = 3, which = 'LM')[1])
#A = self.build_hessian()
#x, y = np.linalg.eig(A)
#s, v, d = np.linalg.svd(A)
#print(sorted(x))
#print(sorted(v))
x, info = scipy.sparse.linalg.cg(Aop, -b, tol = self.tol)
if self.reference == 'rhf':
Ax = at.rhf_to_uhf(self.cepa_A(x), self)
b = at.rhf_to_uhf(b, self)
x = at.rhf_to_uhf(x, self)
energy = self.hf_energy + 2*x.T.dot(b) + x.T.dot(Ax)
else:
energy = self.hf_energy + 2*x.T.dot(b) + x.T.dot(self.cepa_A(x))
return energy
def lagrangian(self, x):
self.lam = .5*x.T.dot(x)
self.lam = 0
b = self.cepa_b()
b = at.collapse_tensor(b, self)
b = at.concatenate_amps(b, self)
if self.reference == 'rhf':
Ax = at.rhf_to_uhf(self.cepa_A(x), self)
b = at.rhf_to_uhf(b, self)
x = at.rhf_to_uhf(x, self)
return abs(np.linalg.norm(Ax+b))
else:
return abs(np.linalg.norm(self.cepa_A(x)+b))
def c3epa_energy(self, x):
b = self.cepa_b()
b = at.collapse_tensor(b, self)
b = at.concatenate_amps(b, self)
if self.reference == 'rhf':
Ax = at.rhf_to_uhf(self.c3epa_A(x), self)
b = at.rhf_to_uhf(b, self)
x = at.rhf_to_uhf(x, self)
energy = self.hf_energy + 2*x.T.dot(b) + x.T.dot(Ax)
else:
energy = self.hf_energy + 2*x.T.dot(b) + x.T.dot(self.c3epa_A(x))
return energy
def c3epa(self, **kwargs):
b = self.cepa_b()
b = at.collapse_tensor(b, self)
b = at.concatenate_amps(b, self)
Aop = scipy.sparse.linalg.LinearOperator((len(b), len(b)), matvec = self.c3epa_A, rmatvec = self.c3epa_A)
x, info = np.array(scipy.sparse.linalg.cg(Aop, -b, tol = self.tol ))
if self.reference == 'rhf':
Ax = at.rhf_to_uhf(self.c3epa_A(x), self)
b = at.rhf_to_uhf(b, self)
x = at.rhf_to_uhf(x, self)
energy = self.hf_energy + 2*x.T.dot(b) + x.T.dot(Ax)
else:
energy = self.hf_energy + 2*x.T.dot(b) + x.T.dot(self.c3epa_A(x))
return energy
def shifted_cepa(self):
b = self.cepa_b()
b = at.collapse_tensor(b, self)
b = at.concatenate_amps(b, self)
norm = 1
old = b*0
self.Ec = 0
x = 0*b
self.x = copy.copy(x)
while abs(norm)>1e-18:
Aop = scipy.sparse.linalg.LinearOperator((len(b), len(b)), matvec = self.shifted_A, rmatvec = self.shifted_A)
x, info = scipy.sparse.linalg.cg(Aop, -b, tol = self.tol, x0 = x)
if self.reference == 'rhf':
norm = at.rhf_to_uhf(old-x, self).dot(at.rhf_to_uhf(old-x, self))
else:
norm = (old-x).dot(old-x)
old = copy.copy(x)
x0 = copy.copy(x)
if self.reference == 'rhf':
#print(x2)
if self.shift == 'ucc3':
Ax2 = self.shifted_A(x)
#print(Ax2)
#energy = self.hf_energy + 2*x2.T.dot(b2) + x2.T.dot(Ax2)-(4/3)*x2.T.dot(xdiag).dot(xdiag).dot(b2)
energy = self.ucc3_energy(x)
#print(at.rhf_to_uhf(self.shifted_A(x), self))
else:
b2 = at.rhf_to_uhf(b, self)
x2 = at.rhf_to_uhf(x, self)
Ax2 = at.rhf_to_uhf(self.shifted_A(x), self)
energy = self.hf_energy + 2*x2.T.dot(b2) + x2.T.dot(Ax2)
else:
if self.shift == 'ucc3':
#print(self.shifted_A(x))
energy = self.ucc3_energy(x)
else:
energy = self.hf_energy + 2*x.T.dot(b) + x.T.dot(self.shifted_A(x))
self.x = copy.copy(x)
self.Ec = energy-self.hf_energy
return energy
def cepa_A(self, x):
if self.reference == 'rhf':
x = at.rhf_to_uhf(x, self)
x = at.decatenate_amps(x, self, reference = 'uhf')
x = at.expand_vector(x, self, reference = 'uhf')
#Initialize Hessian Shapes
Ax = {}
Ax['a'] = np.zeros((self.noa, self.nva))
Ax['b'] = np.zeros((self.nob, self.nvb))
Ax['aa'] = np.zeros((self.noa, self.noa, self.nva, self.nva))
Ax['ab'] = np.zeros((self.noa, self.nob, self.nva, self.nvb))
Ax['bb'] = np.zeros((self.nob, self.nob, self.nvb, self.nvb))
#S->S F (Particle Interaction)
Ax['a'] += contract('ab,ib->ia', self.fa[self.noa:, self.noa:], x['a'])
if self.reference != 'rhf':
Ax['b'] += contract('ab,ib->ia', self.fb[self.nob:, self.nob:], x['b'])
#S->S F (Hole Interaction)
Ax['a'] -= contract('ji,ja->ia', self.fa[:self.noa, :self.noa], x['a'])
if self.reference != 'rhf':
Ax['b'] -= contract('ji,ja->ia', self.fb[:self.nob, :self.nob], x['b'])
#S->S V
Ax['a'] += contract('jabi,jb->ia', self.l_aaaa[:self.noa, self.noa:, self.noa:, :self.noa], x['a'])
Ax['a'] += contract('ajib,jb->ia', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['b'])
if self.reference != 'rhf':
Ax['b'] += contract('jabi,jb->ia', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['a'])
Ax['b'] += contract('jabi,jb->ia', self.l_bbbb[:self.nob, self.nob:, self.nob:, :self.nob], x['b'])
#S->D V (Hole Interaction)
Ax['aa'] -= contract('kbij,ka->ijab', self.l_aaaa[:self.noa, self.noa:, :self.noa, :self.noa], x['a'])
Ax['aa'] += contract('kaij,kb->ijab', self.l_aaaa[:self.noa, self.noa:, :self.noa, :self.noa], x['a'])
Ax['ab'] -= contract('kbij,ka->ijab', self.j_abab[:self.noa, self.nob:, :self.noa, :self.nob], x['a'])
Ax['ab'] -= contract('akij,kb->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, :self.nob], x['b'])
if self.reference != 'rhf':
Ax['bb'] -= contract('kbij,ka->ijab', self.l_bbbb[:self.nob, self.nob:, :self.nob, :self.nob], x['b'])
Ax['bb'] += contract('kaij,kb->ijab', self.l_bbbb[:self.nob, self.nob:, :self.nob, :self.nob], x['b'])
#S->D V (Particle Interaction)
Ax['aa'] += contract('abcj,ic->ijab', self.l_aaaa[self.noa:, self.noa:, self.noa:, :self.noa], x['a'])
Ax['aa'] -= contract('abci,jc->ijab', self.l_aaaa[self.noa:, self.noa:, self.noa:, :self.noa], x['a'])
Ax['ab'] += contract('abcj,ic->ijab', self.j_abab[self.noa:, self.nob:, self.noa:, :self.nob], x['a'])
Ax['ab'] += contract('abic,jc->ijab', self.j_abab[self.noa:, self.nob:, :self.noa, self.nob:], x['b'])
if self.reference != 'rhf':
Ax['bb'] += contract('abcj,ic->ijab', self.l_bbbb[self.nob:, self.nob:, self.nob:, :self.nob], x['b'])
Ax['bb'] -= contract('abci,jc->ijab', self.l_bbbb[self.nob:, self.nob:, self.nob:, :self.nob], x['b'])
#D->S V (Hole Interaction)
rt2 = np.sqrt(2)
'''
Ax['a'] -= .5*contract('kjib,kjab->ia', self.l_aaaa[:self.noa, :self.noa, :self.noa, self.noa:], x['aa'])
Ax['a'] -= contract('kjib,kjab->ia', self.j_abab[:self.noa, :self.nob, :self.noa, self.nob:], x['ab'])
if self.reference != 'rhf':
Ax['b'] -= .5*contract('kjib,kjab->ia', self.l_bbbb[:self.nob, :self.nob, :self.nob, self.nob:], x['bb'])
Ax['b'] -= contract('jkbi,jkba->ia', self.j_abab[:self.noa, :self.nob, self.noa:, :self.nob], x['ab'])
'''
if self.reference != 'rhf':
Ax['a'] -= .5*contract('kjib,kjab->ia', self.l_aaaa[:self.noa, :self.noa, :self.noa, self.noa:], x['aa'])
Ax['a'] -= contract('kjib,kjab->ia', self.j_abab[:self.noa, :self.nob, :self.noa, self.nob:], x['ab'])
Ax['b'] -= .5*contract('kjib,kjab->ia', self.l_bbbb[:self.nob, :self.nob, :self.nob, self.nob:], x['bb'])
Ax['b'] -= contract('jkbi,jkba->ia', self.j_abab[:self.noa, :self.nob, self.noa:, :self.nob], x['ab'])
else:
Ax['a'] -= 1/2 * .5*contract('kjib,kjab->ia', self.l_aaaa[:self.noa, :self.noa, :self.noa, self.noa:], x['aa'])
Ax['a'] -= 1/2 * contract('kjib,kjab->ia', self.j_abab[:self.noa, :self.nob, :self.noa, self.nob:], x['ab'])
Ax['a'] -= 1/2 * .5*contract('kjib,kjab->ia', self.l_bbbb[:self.nob, :self.nob, :self.nob, self.nob:], x['bb'])
Ax['a'] -= 1/2 * contract('jkbi,jkba->ia', self.j_abab[:self.noa, :self.nob, self.noa:, :self.nob], x['ab'])
#D->S V (Particle Interaction)
'''
Ax['a'] += .5*contract('ajcb,ijcb->ia', self.l_aaaa[self.noa:, :self.noa, self.noa:, self.noa:], x['aa'])
Ax['a'] += contract('ajcb,ijcb->ia', self.j_abab[self.noa:, :self.nob, self.noa:, self.nob:], x['ab'])
if self.reference != 'rhf':
Ax['b'] += .5*contract('ajcb,ijcb->ia', self.l_bbbb[self.nob:, :self.nob, self.nob:, self.nob:], x['bb'])
Ax['b'] += contract('jabc,jibc->ia', self.j_abab[:self.noa, self.nob:, self.noa:, self.nob:], x['ab'])
'''
if self.reference != 'rhf':
Ax['a'] += .5*contract('ajcb,ijcb->ia', self.l_aaaa[self.noa:, :self.noa, self.noa:, self.noa:], x['aa'])
Ax['a'] += contract('ajcb,ijcb->ia', self.j_abab[self.noa:, :self.nob, self.noa:, self.nob:], x['ab'])
Ax['b'] += .5*contract('ajcb,ijcb->ia', self.l_bbbb[self.nob:, :self.nob, self.nob:, self.nob:], x['bb'])
Ax['b'] += contract('jabc,jibc->ia', self.j_abab[:self.noa, self.nob:, self.noa:, self.nob:], x['ab'])
else:
Ax['a'] += 1/2 * .5*contract('ajcb,ijcb->ia', self.l_aaaa[self.noa:, :self.noa, self.noa:, self.noa:], x['aa'])
Ax['a'] += 1/2 * contract('ajcb,ijcb->ia', self.j_abab[self.noa:, :self.nob, self.noa:, self.nob:], x['ab'])
Ax['a'] += 1/2 * .5*contract('ajcb,ijcb->ia', self.l_bbbb[self.nob:, :self.nob, self.nob:, self.nob:], x['bb'])
Ax['a'] += 1/2 * contract('jabc,jibc->ia', self.j_abab[:self.noa, self.nob:, self.noa:, self.nob:], x['ab'])
#D->D F (Hole Interaction)
'''
Ax['aa'] -= (contract('kj,ikab->ijab', self.fa[:self.noa, :self.noa], x['aa']))
Ax['aa'] += (contract('ki,jkab->ijab', self.fa[:self.noa, :self.noa], x['aa']))
Ax['ab'] -= contract('kj,ikab->ijab', self.fb[:self.nob, :self.nob], x['ab'])
Ax['ab'] -= contract('ki,kjab->ijab', self.fa[:self.noa, :self.noa], x['ab'])
if self.reference != 'rhf':
Ax['bb'] -= (contract('kj,ikab->ijab', self.fb[:self.nob, :self.nob], x['bb']))
Ax['bb'] += (contract('ki,jkab->ijab', self.fb[:self.nob, :self.nob], x['bb']))
'''
Ax['ab'] -= contract('kj,ikab->ijab', self.fb[:self.nob, :self.nob], x['ab'])
Ax['ab'] -= contract('ki,kjab->ijab', self.fa[:self.noa, :self.noa], x['ab'])
if self.reference != 'rhf':
Ax['aa'] -= (contract('kj,ikab->ijab', self.fa[:self.noa, :self.noa], x['aa']))
Ax['aa'] += (contract('ki,jkab->ijab', self.fa[:self.noa, :self.noa], x['aa']))
Ax['bb'] -= (contract('kj,ikab->ijab', self.fb[:self.nob, :self.nob], x['bb']))
Ax['bb'] += (contract('ki,jkab->ijab', self.fb[:self.nob, :self.nob], x['bb']))
else:
Ax['aa'] -= .5*(contract('kj,ikab->ijab', self.fa[:self.noa, :self.noa], x['aa']))
Ax['aa'] += .5*(contract('ki,jkab->ijab', self.fa[:self.noa, :self.noa], x['aa']))
Ax['aa'] -= .5*(contract('kj,ikab->ijab', self.fb[:self.nob, :self.nob], x['bb']))
Ax['aa'] += .5*(contract('ki,jkab->ijab', self.fb[:self.nob, :self.nob], x['bb']))
#D->D F (Particle Interaction)
'''
Ax['aa'] += contract('bc,ijac->ijab', self.fa[self.noa:, self.noa:], x['aa'])
Ax['aa'] -= contract('ac,ijbc->ijab', self.fa[self.noa:, self.noa:], x['aa'])
Ax['ab'] += contract('bc,ijac->ijab', self.fb[self.nob:, self.nob:], x['ab'])
Ax['ab'] += contract('ac,ijcb->ijab', self.fa[self.noa:, self.noa:], x['ab'])
if self.reference != 'rhf':
Ax['bb'] += contract('bc,ijac->ijab', self.fb[self.nob:, self.nob:], x['bb'])
Ax['bb'] -= contract('ac,ijbc->ijab', self.fb[self.nob:, self.nob:], x['bb'])
'''
Ax['ab'] += contract('bc,ijac->ijab', self.fb[self.nob:, self.nob:], x['ab'])
Ax['ab'] += contract('ac,ijcb->ijab', self.fa[self.noa:, self.noa:], x['ab'])
if self.reference != 'rhf':
Ax['aa'] += contract('bc,ijac->ijab', self.fa[self.noa:, self.noa:], x['aa'])
Ax['aa'] -= contract('ac,ijbc->ijab', self.fa[self.noa:, self.noa:], x['aa'])
Ax['bb'] += contract('bc,ijac->ijab', self.fb[self.nob:, self.nob:], x['bb'])
Ax['bb'] -= contract('ac,ijbc->ijab', self.fb[self.nob:, self.nob:], x['bb'])
else:
Ax['aa'] += .5*contract('bc,ijac->ijab', self.fa[self.noa:, self.noa:], x['aa'])
Ax['aa'] -= .5*contract('ac,ijbc->ijab', self.fa[self.noa:, self.noa:], x['aa'])
Ax['aa'] += .5*contract('bc,ijac->ijab', self.fb[self.nob:, self.nob:], x['bb'])
Ax['aa'] -= .5*contract('ac,ijbc->ijab', self.fb[self.nob:, self.nob:], x['bb'])
#D->D V (Particle, Particle Interaction)
Ax['aa'] += .5*contract('abcd,ijcd->ijab', self.l_aaaa[self.noa:, self.noa:, self.noa:, self.noa:], x['aa'])
Ax['ab'] += .5*contract('abcd,ijcd->ijab', self.j_abab[self.noa:, self.nob:, self.noa:, self.nob:], x['ab'])
Ax['ab'] += .5*contract('abdc,ijdc->ijab', self.j_abab[self.noa:, self.nob:, self.noa:, self.nob:], x['ab'])
if self.reference != 'rhf':
Ax['bb'] += .5*contract('abcd,ijcd->ijab', self.l_bbbb[self.nob:, self.nob:, self.nob:, self.nob:], x['bb'])
'''
Ax['ab'] += .5*contract('abcd,ijcd->ijab', self.j_abab[self.noa:, self.nob:, self.noa:, self.nob:], x['ab'])
Ax['ab'] += .5*contract('abdc,ijdc->ijab', self.j_abab[self.noa:, self.nob:, self.noa:, self.nob:], x['ab'])
if self.reference != 'rhf':
Ax['aa'] += .5*contract('abcd,ijcd->ijab', self.l_aaaa[self.noa:, self.noa:, self.noa:, self.noa:], x['aa'])
Ax['bb'] += .5*contract('abcd,ijcd->ijab', self.l_bbbb[self.nob:, self.nob:, self.nob:, self.nob:], x['bb'])
else:
Ax['aa'] += .5*.5*contract('abcd,ijcd->ijab', self.l_aaaa[self.noa:, self.noa:, self.noa:, self.noa:], x['aa'])
Ax['aa'] += .5*.5*contract('abcd,ijcd->ijab', self.l_bbbb[self.nob:, self.nob:, self.nob:, self.nob:], x['bb'])
'''
#D->D V (Hole, Hole Interaction)
Ax['aa'] += .5*contract('ijkl,klab->ijab', self.l_aaaa[:self.noa, :self.noa, :self.noa, :self.noa], x['aa'])
Ax['ab'] += .5*contract('ijkl,klab->ijab', self.j_abab[:self.noa, :self.nob, :self.noa, :self.nob], x['ab'])
Ax['ab'] += .5*contract('ijlk,lkab->ijab', self.j_abab[:self.noa, :self.nob, :self.noa, :self.nob], x['ab'])
if self.reference != 'rhf':
Ax['bb'] += .5*contract('ijkl,klab->ijab', self.l_bbbb[:self.nob, :self.nob, :self.nob, :self.nob], x['bb'])
'''
Ax['ab'] += .5*contract('ijkl,klab->ijab', self.j_abab[:self.noa, :self.nob, :self.noa, :self.nob], x['ab'])
Ax['ab'] += .5*contract('ijlk,lkab->ijab', self.j_abab[:self.noa, :self.nob, :self.noa, :self.nob], x['ab'])
if self.reference != 'rhf':
Ax['aa'] += .5*contract('ijkl,klab->ijab', self.l_aaaa[:self.noa, :self.noa, :self.noa, :self.noa], x['aa'])
Ax['bb'] += .5*contract('ijkl,klab->ijab', self.l_bbbb[:self.nob, :self.nob, :self.nob, :self.nob], x['bb'])
else:
Ax['aa'] += .5*.5*contract('ijkl,klab->ijab', self.l_aaaa[:self.noa, :self.noa, :self.noa, :self.noa], x['aa'])
Ax['aa'] += .5*.5*contract('ijkl,klab->ijab', self.l_bbbb[:self.nob, :self.nob, :self.nob, :self.nob], x['bb'])
'''
#D->D V (Hole, Particle Interaction)
'''
Ax['aa'] -= contract('akcj,ikcb->ijab', self.l_aaaa[self.noa:, :self.noa, self.noa:, :self.noa], x['aa'])
Ax['aa'] += contract('bkcj,ikca->ijab', self.l_aaaa[self.noa:, :self.noa, self.noa:, :self.noa], x['aa'])
Ax['aa'] += contract('akci,jkcb->ijab', self.l_aaaa[self.noa:, :self.noa, self.noa:, :self.noa], x['aa'])
Ax['aa'] -= contract('bkci,jkca->ijab', self.l_aaaa[self.noa:, :self.noa, self.noa:, :self.noa], x['aa'])
Ax['aa'] -= contract('akjc,ikbc->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['ab'])
Ax['aa'] += contract('bkjc,ikac->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['ab'])
Ax['aa'] += contract('akic,jkbc->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['ab'])
Ax['aa'] -= contract('bkic,jkac->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['ab'])
Ax['ab'] -= contract('akcj,ikcb->ijab', self.j_abab[self.noa:, :self.nob, self.noa:, :self.nob], x['ab'])
Ax['ab'] -= contract('kbcj,ikca->ijab', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['aa'])
Ax['ab'] += contract('akic,kjcb->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['bb'])
Ax['ab'] -= contract('kbic,kjac->ijab', self.j_abab[:self.noa, self.nob:, :self.noa, self.nob:], x['ab'])
Ax['ab'] += contract('kbcj,ikac->ijab', self.l_bbbb[:self.nob, self.nob:, self.nob:, :self.nob], x['ab'])
Ax['ab'] -= contract('akci,kjcb->ijab', self.l_aaaa[self.noa:, :self.noa, self.noa:, :self.noa], x['ab'])
if self.reference != 'rhf':
Ax['bb'] -= contract('akcj,ikcb->ijab', self.l_bbbb[self.nob:, :self.nob, self.nob:, :self.nob], x['bb'])
Ax['bb'] += contract('bkcj,ikca->ijab', self.l_bbbb[self.nob:, :self.nob, self.nob:, :self.nob], x['bb'])
Ax['bb'] += contract('akci,jkcb->ijab', self.l_bbbb[self.nob:, :self.nob, self.nob:, :self.nob], x['bb'])
Ax['bb'] -= contract('bkci,jkca->ijab', self.l_bbbb[self.nob:, :self.nob, self.nob:, :self.nob], x['bb'])
Ax['bb'] -= contract('kacj,kicb->ijab', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['ab'])
Ax['bb'] += contract('kbcj,kica->ijab', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['ab'])
Ax['bb'] += contract('kaci,kjcb->ijab', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['ab'])
Ax['bb'] -= contract('kbci,kjca->ijab', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['ab'])
'''
Ax['ab'] -= contract('akcj,ikcb->ijab', self.j_abab[self.noa:, :self.nob, self.noa:, :self.nob], x['ab'])
Ax['ab'] -= contract('kbcj,ikca->ijab', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['aa'])
Ax['ab'] += contract('akic,kjcb->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['bb'])
Ax['ab'] -= contract('kbic,kjac->ijab', self.j_abab[:self.noa, self.nob:, :self.noa, self.nob:], x['ab'])
Ax['ab'] += contract('kbcj,ikac->ijab', self.l_bbbb[:self.nob, self.nob:, self.nob:, :self.nob], x['ab'])
Ax['ab'] -= contract('akci,kjcb->ijab', self.l_aaaa[self.noa:, :self.noa, self.noa:, :self.noa], x['ab'])
if self.reference != 'rhf':
Ax['aa'] -= contract('akcj,ikcb->ijab', self.l_aaaa[self.noa:, :self.noa, self.noa:, :self.noa], x['aa'])
Ax['aa'] += contract('bkcj,ikca->ijab', self.l_aaaa[self.noa:, :self.noa, self.noa:, :self.noa], x['aa'])
Ax['aa'] += contract('akci,jkcb->ijab', self.l_aaaa[self.noa:, :self.noa, self.noa:, :self.noa], x['aa'])
Ax['aa'] -= contract('bkci,jkca->ijab', self.l_aaaa[self.noa:, :self.noa, self.noa:, :self.noa], x['aa'])
Ax['aa'] -= contract('akjc,ikbc->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['ab'])
Ax['aa'] += contract('bkjc,ikac->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['ab'])
Ax['aa'] += contract('akic,jkbc->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['ab'])
Ax['aa'] -= contract('bkic,jkac->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['ab'])
Ax['bb'] -= contract('akcj,ikcb->ijab', self.l_bbbb[self.nob:, :self.nob, self.nob:, :self.nob], x['bb'])
Ax['bb'] += contract('bkcj,ikca->ijab', self.l_bbbb[self.nob:, :self.nob, self.nob:, :self.nob], x['bb'])
Ax['bb'] += contract('akci,jkcb->ijab', self.l_bbbb[self.nob:, :self.nob, self.nob:, :self.nob], x['bb'])
Ax['bb'] -= contract('bkci,jkca->ijab', self.l_bbbb[self.nob:, :self.nob, self.nob:, :self.nob], x['bb'])
Ax['bb'] -= contract('kacj,kicb->ijab', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['ab'])
Ax['bb'] += contract('kbcj,kica->ijab', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['ab'])
Ax['bb'] += contract('kaci,kjcb->ijab', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['ab'])
Ax['bb'] -= contract('kbci,kjca->ijab', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['ab'])
else:
Ax['aa'] -= .5*contract('akcj,ikcb->ijab', self.l_aaaa[self.noa:, :self.noa, self.noa:, :self.noa], x['aa'])
Ax['aa'] += .5*contract('bkcj,ikca->ijab', self.l_aaaa[self.noa:, :self.noa, self.noa:, :self.noa], x['aa'])
Ax['aa'] += .5*contract('akci,jkcb->ijab', self.l_aaaa[self.noa:, :self.noa, self.noa:, :self.noa], x['aa'])
Ax['aa'] -= .5*contract('bkci,jkca->ijab', self.l_aaaa[self.noa:, :self.noa, self.noa:, :self.noa], x['aa'])
Ax['aa'] -= .5*contract('akjc,ikbc->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['ab'])
Ax['aa'] += .5*contract('bkjc,ikac->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['ab'])
Ax['aa'] += .5*contract('akic,jkbc->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['ab'])
Ax['aa'] -= .5*contract('bkic,jkac->ijab', self.j_abab[self.noa:, :self.nob, :self.noa, self.nob:], x['ab'])
Ax['aa'] -= .5*contract('akcj,ikcb->ijab', self.l_bbbb[self.nob:, :self.nob, self.nob:, :self.nob], x['bb'])
Ax['aa'] += .5*contract('bkcj,ikca->ijab', self.l_bbbb[self.nob:, :self.nob, self.nob:, :self.nob], x['bb'])
Ax['aa'] += .5*contract('akci,jkcb->ijab', self.l_bbbb[self.nob:, :self.nob, self.nob:, :self.nob], x['bb'])
Ax['aa'] -= .5*contract('bkci,jkca->ijab', self.l_bbbb[self.nob:, :self.nob, self.nob:, :self.nob], x['bb'])
Ax['aa'] -= .5*contract('kacj,kicb->ijab', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['ab'])
Ax['aa'] += .5*contract('kbcj,kica->ijab', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['ab'])
Ax['aa'] += .5*contract('kaci,kjcb->ijab', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['ab'])
Ax['aa'] -= .5*contract('kbci,kjca->ijab', self.j_abab[:self.noa, self.nob:, self.noa:, :self.nob], x['ab'])
Ax = at.collapse_tensor(Ax, self)
Ax = at.concatenate_amps(Ax, self)
return Ax
def __init__(self, geometry, basis, reference, **kwargs):
import psi4
self.optimize = False
self.scf = False
self.mp2 = False
self.bfgs_ic3epa = False
self.ccsd = False
self.cepa1 = False
self.ccsdpt = False
self.cepa0 = False
self.shucc = False
self.lam_cepa = None
self.lccd = False
self.acpf = False
self.psi_acpf = False
self.psi_aqcc = False
self.psi_cepa0 = False
self.olccd_iters = 50
self.uacpf = False
self.aqcc = False
self.uaqcc = False
self.run_ic3epa = False
self.ocepa = False
self.fci = False
self.d_convergence = 1e-6
self.r_convergence = 1e-5
self.run_svd = False
self.sys_name = "Unnamed system:"
self.ucc3 = False
self.tol = 1e-14
self.log_file = 'out.dat'
self.mem = '24GB'
for key, value in kwargs.items():
setattr(self, key, value)
try:
assert reference == 'rhf' or reference == 'uhf'
except:
print("Only \"rhf\" or \"uhf\" allowed.")
exit()
self.reference = reference
print(self.sys_name)
psi4.geometry(geometry)
#psi4.core.be_quiet()
psi4.core.clean()
if os.path.exists(self.log_file):
cha = 'a'
else:
cha = 'w'
log = open(self.log_file, cha)
log.write(self.sys_name)
psi4.set_memory(self.mem)
if self.optimize != False:
psi4.set_options({'reference': self.reference, 'scf_type': 'pk', 'g_convergence': 'GAU_TIGHT', 'd_convergence': self.d_convergence})
psi4.set_options({'opt_coordinates': self.optimize, 'geom_maxiter': 500, 'mp2_type': 'conv'})
#Some intermediates tweaked to converge problem systems, final optimization obviously kept the same.
#E, wfnopt = psi4.optimize('scf/6-311G(d,p)', return_wfn = True)
#E, wfnopt = psi4.optimize('mp2/6-311G(d,p)', return_wfn = True)
E, wfnopt = psi4.optimize('b3lyp/6-311G(d,p)', return_wfn = True)
log.write((wfnopt.molecule().create_psi4_string_from_molecule()))
psi4.set_options({'reference': reference, 'basis': basis, 'd_convergence': self.d_convergence, 'scf_type': 'pk', 'r_convergence': self.r_convergence, 'maxiter': 100, 'cc_type': 'conv', 'mo_maxiter': self.mo_maxiter})
self.hf_energy, wfn = psi4.energy('scf', return_wfn = True)
if self.scf == True:
print("HF energy:".ljust(30)+("{0:20.16f}".format(self.hf_energy)))
if self.mp2 == True:
print("MP2 energy:".ljust(30)+("{0:20.16f}".format(psi4.energy('mp2'))))
if self.ccsd == True:
print("CCSD energy:".ljust(30)+("{0:20.16f}".format(psi4.energy('ccsd'))))
if self.ccsdpt == True:
print("CCSD(T) energy:".ljust(30)+("{0:20.16f}".format(psi4.energy('ccsd(t)'))))
if self.lccd == True:
print("LCCD energy:".ljust(30)+("{0:20.16f}".format(psi4.energy('lccd'))))
if self.cepa1 == True and self.reference == 'rhf':
print("CEPA(1) energy:".ljust(30)+("{0:20.16f}".format(psi4.energy('cepa(1)'))))
if self.ocepa == True:
print("OCEPA energy:".ljust(30)+("{0:20.16f}".format(psi4.energy('olccd'))))
if self.fci == True:
print("FCI energy:".ljust(30)+("{0:20.16f}".format(psi4.energy('fci'))))
if self.psi_acpf == True:
print("ACPF energy:".ljust(30)+("{0:20.16f}".format(psi4.energy('acpf'))))
if self.psi_aqcc == True:
print("AQCC energy:".ljust(30)+("{0:20.16f}".format(psi4.energy('aqcc'))))
if self.psi_cepa0 == True:
print("CEPA(0) energy:".ljust(30)+("{0:20.16f}".format(psi4.energy('cepa(0)'))))
mints = psi4.core.MintsHelper(wfn.basisset())
ca = wfn.Ca()
cb = wfn.Cb()
self.fa = wfn.Fa()
self.fb = wfn.Fb()
self.j_aaaa = np.array(mints.mo_eri(ca, ca, ca, ca))
self.j_abab = np.array(mints.mo_eri(ca, ca, cb, cb))
self.j_baba = np.array(mints.mo_eri(cb, cb, ca, ca))
self.j_bbbb = np.array(mints.mo_eri(cb, cb, cb, cb))
self.fa.transform(ca)
if reference != 'rhf':
self.fb.transform(cb)
self.fa = np.array(self.fa)
self.fb = np.array(self.fb)
self.j_aaaa = self.j_aaaa.swapaxes(1, 2)
self.j_abab = self.j_abab.swapaxes(1, 2)
self.j_baba = self.j_baba.swapaxes(1, 2)
self.j_bbbb = self.j_bbbb.swapaxes(1, 2)
k_aaaa = copy.copy(self.j_aaaa)
k_bbbb = copy.copy(self.j_bbbb)
k_aaaa = k_aaaa.swapaxes(2, 3)
k_bbbb = k_bbbb.swapaxes(2, 3)
self.l_aaaa = self.j_aaaa - k_aaaa
self.l_bbbb = self.j_bbbb - k_bbbb
self.noa = wfn.Ca_subset("AO", "ACTIVE_OCC").shape[1]
self.nob = wfn.Cb_subset("AO", "ACTIVE_OCC").shape[1]
self.nva = wfn.Ca_subset("AO", "ACTIVE_VIR").shape[1]
self.nvb = wfn.Cb_subset("AO", "ACTIVE_VIR").shape[1]
self.aopairs = np.triu_indices(self.noa, k=1)
self.avpairs = np.triu_indices(self.nva, k=1)
self.bopairs = np.triu_indices(self.nob, k=1)
self.bvpairs = np.triu_indices(self.nvb, k=1)
psi4.core.clean()
self.b = self.cepa_b()
self.b = at.collapse_tensor(self.b, self)
self.b = at.concatenate_amps(self.b, self)
if self.cepa0 == True:
cepa = self.cepa()
print("CEPA(0) energy:".ljust(30)+("{0:20.16f}".format(cepa)))
if self.acpf == True:
self.s2_term = False
self.shift = 'acpf'
acpf = self.shifted_cepa()
print("ACPF energy:".ljust(30)+("{0:20.16f}".format(acpf)))
if self.aqcc == True:
self.s2_term = False
self.shift = 'aqcc'
aqcc = self.shifted_cepa()
print("AQCC energy:".ljust(30)+("{0:20.16f}".format(aqcc)))
if self.shucc == True:
self.lam = 1
c3epa = self.c3epa()
print("UCC-2 energy:".ljust(30)+("{0:20.16f}".format(c3epa)))
'''
if self.ucc3 == True:
self.lam = 1
b = self.b
x = 0*b
#res = scipy.optimize.minimize(self.ucc3_energy, x, jac = self.ucc3_gradient, method = 'bfgs', options = {'gtol': 1e-5, 'disp': True})
#res = scipy.optimize.minimize(self.ucc3_energy, x, jac = self.numerical_ucc3_gradient, method = 'bfgs', options = {'gtol': 1e-5, 'disp': True})
res = scipy.optimize.minimize(self.ucc3_energy, x, jac = None, method = 'bfgs', options = {'gtol': 1e-9, 'disp': True})
print("UCC(3) energy:".ljust(30)+("{0:20.16f}".format(res.fun)))
self.x = res.x
x = res.x
self.shift = 'ucc3'
if self.reference == 'rhf':
x2 = at.rhf_to_uhf(x, self)
shift = []
for i in range(0, len(x2)):
shift.append(x2[i]**2)
shift = np.array(shift)
shift = at.uhf_to_rhf(shift, self)
else:
shift = []
for i in range(0, len(x)):
shift.append(x[i]**2)
shift = np.array(shift)
#print('shift')
#print(shift)
#print('gradient')
#print(self.shifted_A(x)+self.b)
'''
if self.lam_cepa != None:
self.lam = self.lam_cepa
c3epa = self.c3epa()
print("λ-C3EPA energy:".ljust(30)+("{0:20.16f}".format(c3epa)))
if self.run_ic3epa == True:
self.lam = 0
c3epa = self.ic3epa()
#print("IC3EPA energy:".ljust(30)+("{0:20.16f}".format(c3epa)))
if self.uacpf == True:
self.s2_term = True
self.shift = 'acpf'
uacpf = self.shifted_cepa()
print("UACPF energy:".ljust(30)+("{0:20.16f}".format(uacpf)))
if self.uaqcc == True:
self.s2_term = True
self.shift = 'aqcc'
uaqcc = self.shifted_cepa()
print("UAQCC energy:".ljust(30)+("{0:20.16f}".format(uaqcc)))
if self.ucc3 == True:
self.lam = 1
self.shift = 'ucc3'
ucc3 = self.shifted_cepa()
print("UCC(3) energy:".ljust(30)+("{0:20.16f}".format(ucc3)))
if self.bfgs_ic3epa == True:
b = self.cepa_b()
b = at.collapse_tensor(b, self)
b = at.concatenate_amps(b, self)
x = 0*b
res = scipy.optimize.minimize(self.bfgs_ic3epa_energy, x, method = 'bfgs', options = {'gtol': 1e-10})
print("Variational IC3EPA energy:".ljust(30)+("{0:20.16f}".format(self.bfgs_ic3epa_energy(res.x))))
