#!/usr/bin/env python
# Copyright 2014-2020 The PySCF Developers. All Rights Reserved.
#
# Licensed under the Apache License, Version 2.0 (the "License");
# you may not use this file except in compliance with the License.
# You may obtain a copy of the License at
#
# http://www.apache.org/licenses/LICENSE-2.0
#
# Unless required by applicable law or agreed to in writing, software
# distributed under the License is distributed on an "AS IS" BASIS,
# WITHOUT WARRANTIES OR CONDITIONS OF ANY KIND, either express or implied.
# See the License for the specific language governing permissions and
# limitations under the License.
#
# Author: Yang Gao <younggao1994@gmail.com>
#
'''
Non-relativistic analytical nuclear gradients for restricted Hartree Fock with kpoints sampling
'''
import numpy as np
from pyscf import lib
from pyscf.lib import logger
from pyscf.grad import rhf as molgrad
from pyscf.pbc.gto.pseudo.pp import get_vlocG, get_alphas, get_projG, projG_li, _qli
from pyscf.pbc.dft.numint import eval_ao_kpts
from pyscf.pbc import gto, tools
from pyscf.gto import mole
import scipy
[docs]
def grad_elec(mf_grad, mo_energy=None, mo_coeff=None, mo_occ=None, atmlst=None):
'''
Electronic part of KRHF/KRKS gradients
Args:
mf_grad : pbc.grad.krhf.Gradients or pbc.grad.krks.Gradients object
'''
mf = mf_grad.base
cell = mf_grad.cell
kpts = mf.kpts
nkpts = len(kpts)
if mo_energy is None: mo_energy = mf.mo_energy
if mo_occ is None: mo_occ = mf.mo_occ
if mo_coeff is None: mo_coeff = mf.mo_coeff
if atmlst is None: atmlst = range(cell.natm)
log = logger.Logger(mf_grad.stdout, mf_grad.verbose)
hcore_deriv = mf_grad.hcore_generator(cell, kpts)
s1 = mf_grad.get_ovlp(cell, kpts)
dm0 = mf.make_rdm1(mo_coeff, mo_occ)
t0 = (logger.process_clock(), logger.perf_counter())
log.debug('Computing Gradients of NR-HF Coulomb repulsion')
vhf = mf_grad.get_veff(dm0, kpts)
log.timer('gradients of 2e part', *t0)
dme0 = mf_grad.make_rdm1e(mo_energy, mo_coeff, mo_occ)
aoslices = cell.aoslice_by_atom()
de = np.zeros([len(atmlst),3])
for x, ia in enumerate(atmlst):
p0, p1 = aoslices[ia,2:]
h1ao = hcore_deriv(ia)
de[x] += np.einsum('xkij,kji->x', h1ao, dm0).real
# nabla was applied on bra in vhf, *2 for the contributions of nabla|ket>
de[x] += np.einsum('xkij,kji->x', vhf[:,:,p0:p1], dm0[:,:,p0:p1]).real * 2
de[x] -= np.einsum('kxij,kji->x', s1[:,:,p0:p1], dme0[:,:,p0:p1]).real * 2
de[x] /= nkpts
de[x] += mf_grad.extra_force(ia, locals())
if log.verbose > logger.DEBUG:
log.debug('gradients of electronic part')
mf_grad._write(log, cell, de, atmlst)
return de
def _make_fakemol():
fakemol = mole.Mole()
fakemol._atm = np.zeros((1,mole.ATM_SLOTS), dtype=np.int32)
fakemol._bas = np.zeros((1,mole.BAS_SLOTS), dtype=np.int32)
ptr = mole.PTR_ENV_START
fakemol._env = np.zeros(ptr+10)
fakemol._bas[0,mole.NPRIM_OF ] = 1
fakemol._bas[0,mole.NCTR_OF ] = 1
fakemol._bas[0,mole.PTR_EXP ] = ptr+3
fakemol._bas[0,mole.PTR_COEFF] = ptr+4
return fakemol
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def get_hcore(cell, kpts):
'''Part of the nuclear gradients of core Hamiltonian'''
h1 = np.asarray(cell.pbc_intor('int1e_ipkin', kpts=kpts))
dtype = h1.dtype
if cell._pseudo:
SI=cell.get_SI()
Gv = cell.Gv
natom = cell.natm
coords = cell.get_uniform_grids()
ngrids = len(coords)
vlocG = get_vlocG(cell)
vpplocG = -np.einsum('ij,ij->j', SI, vlocG)
vpplocG[0] = np.sum(get_alphas(cell))
vpplocR = tools.ifft(vpplocG, cell.mesh).real
fakemol = _make_fakemol()
ptr = mole.PTR_ENV_START
for kn, kpt in enumerate(kpts):
aos = eval_ao_kpts(cell, coords, kpt, deriv=1)[0]
vloc = np.einsum('agi,g,gj->aij', aos[1:].conj(), vpplocR, aos[0])
expir = np.exp(-1j*np.dot(coords, kpt))
aokG = np.asarray([tools.fftk(np.asarray(ao.T, order='C'),
cell.mesh, expir).T for ao in aos])
Gk = Gv + kpt
G_rad = lib.norm(Gk, axis=1)
vnl = np.zeros(vloc.shape, dtype=np.complex128)
for ia in range(natom):
symb = cell.atom_symbol(ia)
if symb not in cell._pseudo:
continue
pp = cell._pseudo[symb]
for l, proj in enumerate(pp[5:]):
rl, nl, hl = proj
if nl >0:
hl = np.asarray(hl)
fakemol._bas[0,mole.ANG_OF] = l
fakemol._env[ptr+3] = .5*rl**2
fakemol._env[ptr+4] = rl**(l+1.5)*np.pi**1.25
pYlm_part = fakemol.eval_gto('GTOval', Gk)
pYlm = np.empty((nl,l*2+1,ngrids))
for k in range(nl):
qkl = _qli(G_rad*rl, l, k)
pYlm[k] = pYlm_part.T * qkl
SPG_lmi = np.einsum('g,nmg->nmg', SI[ia].conj(), pYlm)
SPG_lm_aoG = np.einsum('nmg,agp->anmp', SPG_lmi, aokG)
tmp = np.einsum('ij,ajmp->aimp', hl, SPG_lm_aoG[1:])
vnl += np.einsum('aimp,imq->apq', tmp.conj(), SPG_lm_aoG[0])
vnl *= (1./ngrids**2)
if dtype == np.float64:
h1[kn,:] += vloc.real + vnl.real
else:
h1[kn,:] += vloc + vnl
else:
raise NotImplementedError
return h1
[docs]
def get_ovlp(cell, kpts):
return -np.asarray(cell.pbc_intor('int1e_ipovlp', kpts=kpts))
[docs]
def hcore_generator(mf, cell=None, kpts=None):
if cell is None: cell = mf.cell
if kpts is None: kpts = mf.kpts
h1 = get_hcore(cell, kpts)
dtype = h1.dtype
aoslices = cell.aoslice_by_atom()
SI=cell.get_SI() ##[natom ,grid]
mesh = cell.mesh
Gv = cell.Gv ##[grid, 3]
ngrids = len(Gv)
coords = cell.get_uniform_grids()
vlocG = get_vlocG(cell) ###[natom, grid]
ptr = mole.PTR_ENV_START
def hcore_deriv(atm_id):
shl0, shl1, p0, p1 = aoslices[atm_id]
symb = cell.atom_symbol(atm_id)
fakemol = _make_fakemol()
vloc_g = 1j * np.einsum('ga,g->ag', Gv, SI[atm_id]*vlocG[atm_id])
nkpts, nao = h1.shape[0], h1.shape[2]
hcore = np.zeros([3,nkpts,nao,nao], dtype=h1.dtype)
for kn, kpt in enumerate(kpts):
ao = eval_ao_kpts(cell, coords, kpt)[0]
rho = np.einsum('gi,gj->gij',ao.conj(),ao)
for ax in range(3):
vloc_R = tools.ifft(vloc_g[ax], mesh).real
vloc = np.einsum('gij,g->ij', rho, vloc_R)
hcore[ax,kn] += vloc
rho = None
aokG= tools.fftk(np.asarray(ao.T, order='C'),
mesh, np.exp(-1j*np.dot(coords, kpt))).T
ao = None
Gk = Gv + kpt
G_rad = lib.norm(Gk, axis=1)
if symb not in cell._pseudo: continue
pp = cell._pseudo[symb]
for l, proj in enumerate(pp[5:]):
rl, nl, hl = proj
if nl >0:
hl = np.asarray(hl)
fakemol._bas[0,mole.ANG_OF] = l
fakemol._env[ptr+3] = .5*rl**2
fakemol._env[ptr+4] = rl**(l+1.5)*np.pi**1.25
pYlm_part = fakemol.eval_gto('GTOval', Gk)
pYlm = np.empty((nl,l*2+1,ngrids))
for k in range(nl):
qkl = _qli(G_rad*rl, l, k)
pYlm[k] = pYlm_part.T * qkl
SPG_lmi = np.einsum('g,nmg->nmg', SI[atm_id].conj(), pYlm)
SPG_lm_aoG = np.einsum('nmg,gp->nmp', SPG_lmi, aokG)
SPG_lmi_G = 1j * np.einsum('nmg, ga->anmg', SPG_lmi, Gv)
SPG_lm_G_aoG = np.einsum('anmg, gp->anmp', SPG_lmi_G, aokG)
tmp_1 = np.einsum('ij,ajmp->aimp', hl, SPG_lm_G_aoG)
tmp_2 = np.einsum('ij,jmp->imp', hl, SPG_lm_aoG)
vppnl = (np.einsum('imp,aimq->apq', SPG_lm_aoG.conj(), tmp_1) +
np.einsum('aimp,imq->apq', SPG_lm_G_aoG.conj(), tmp_2))
vppnl *=(1./ngrids**2)
if dtype==np.float64:
hcore[:,kn] += vppnl.real
else:
hcore[:,kn] += vppnl
hcore[:,kn,p0:p1] -= h1[kn,:,p0:p1]
hcore[:,kn,:,p0:p1] -= h1[kn,:,p0:p1].transpose(0,2,1).conj()
return hcore
return hcore_deriv
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def grad_nuc(cell, atmlst):
'''
Derivatives of nuclear repulsion energy wrt nuclear coordinates
'''
chargs = cell.atom_charges()
ew_eta, ew_cut = cell.get_ewald_params()
log_precision = np.log(cell.precision / (chargs.sum()*16*np.pi**2))
ke_cutoff = -2*ew_eta**2*log_precision
mesh = cell.cutoff_to_mesh(ke_cutoff)
logger.debug1(cell, 'mesh for ewald %s', mesh)
coords = cell.atom_coords()
Lall = cell.get_lattice_Ls()
natom = len(chargs)
ewovrl_grad = np.zeros([natom,3])
for i, qi in enumerate(chargs):
ri = coords[i]
for j in range(natom):
if j == i:
continue
qj = chargs[j]
rj = coords[j]
r1 = ri-rj + Lall
r = np.sqrt(np.einsum('ji,ji->j', r1, r1))
r = r.reshape(len(r),1)
ewovrl_grad[i] += np.sum(- (qi * qj / r ** 3 * r1 *
scipy.special.erfc(ew_eta * r).reshape(len(r),1)), axis = 0)
ewovrl_grad[i] += np.sum(- qi * qj / r ** 2 * r1 * 2 * ew_eta / np.sqrt(np.pi) *
np.exp(-ew_eta**2 * r ** 2).reshape(len(r),1), axis = 0)
Gv, Gvbase, weights = cell.get_Gv_weights(mesh)
absG2 = np.einsum('gi,gi->g', Gv, Gv)
absG2[absG2==0] = 1e200
ewg_grad = np.zeros([natom,3])
SI = cell.get_SI(Gv)
if cell.low_dim_ft_type is None or cell.dimension == 3:
coulG = 4*np.pi / absG2
coulG *= weights
ZSI = np.einsum("i,ij->j", chargs, SI)
ZexpG2 = coulG * np.exp(-absG2/(4*ew_eta**2))
ZexpG2_mod = ZexpG2.reshape(len(ZexpG2),1) * Gv
for i, qi in enumerate(chargs):
Zfac = np.imag(ZSI * SI[i].conj()) * qi
ewg_grad[i] = - np.sum(Zfac.reshape((len(Zfac),1)) * ZexpG2_mod, axis = 0)
ew_grad = ewg_grad + ewovrl_grad
if atmlst is not None:
ew_grad = ew_grad[atmlst]
return ew_grad
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def get_jk(mf_grad, dm, kpts):
'''J = ((-nabla i) j| kl) D_lk
K = ((-nabla i) j| kl) D_jk
'''
vj, vk = mf_grad.get_jk(dm, kpts)
return vj, vk
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def get_j(mf_grad, dm, kpts):
return mf_grad.get_j(dm, kpts)
[docs]
def get_k(mf_grad, dm, kpts):
return mf_grad.get_k(dm, kpts)
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def get_veff(mf_grad, dm, kpts):
'''NR Hartree-Fock Coulomb repulsion'''
vj, vk = mf_grad.get_jk(dm, kpts)
return vj - vk * .5
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def make_rdm1e(mo_energy, mo_coeff, mo_occ):
'''Energy weighted density matrix'''
nkpts = len(mo_occ)
dm1e = [molgrad.make_rdm1e(mo_energy[k], mo_coeff[k], mo_occ[k]) for k in range(nkpts)]
return np.asarray(dm1e)
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class GradientsBase(molgrad.GradientsBase):
'''
Basic nuclear gradient functions for non-relativistic methods
'''
def __init__(self, method):
self.cell = method.cell
self.kpts = method.kpts
molgrad.GradientsBase.__init__(self, method)
[docs]
def get_hcore(self, cell=None, kpts=None):
if cell is None: cell = self.cell
if kpts is None: kpts = self.kpts
return get_hcore(cell, kpts)
hcore_generator = hcore_generator
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def get_ovlp(self, cell=None, kpts=None):
if cell is None: cell = self.cell
if kpts is None: kpts = self.kpts
return get_ovlp(cell, kpts)
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def get_jk(self, dm=None, kpts=None):
if kpts is None: kpts = self.kpts
if dm is None: dm = self.base.make_rdm1()
exxdiv = self.base.exxdiv
cpu0 = (logger.process_clock(), logger.perf_counter())
vj, vk = self.base.with_df.get_jk_e1(dm, kpts, exxdiv=exxdiv)
logger.timer(self, 'vj and vk', *cpu0)
return vj, vk
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def get_j(self, dm=None, kpts=None):
if kpts is None: kpts = self.kpts
if dm is None: dm = self.base.make_rdm1()
cpu0 = (logger.process_clock(), logger.perf_counter())
vj = self.base.with_df.get_j_e1(dm, kpts)
logger.timer(self, 'vj', *cpu0)
return vj
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def get_k(self, dm=None, kpts=None, kpts_band=None):
if kpts is None: kpts = self.kpts
if dm is None: dm = self.base.make_rdm1()
exxdiv = self.base.exxdiv
cpu0 = (logger.process_clock(), logger.perf_counter())
vk = self.base.with_df.get_k_e1(dm, kpts, kpts_band, exxdiv)
logger.timer(self, 'vk', *cpu0)
return vk
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def grad_nuc(self, cell=None, atmlst=None):
if cell is None: cell = self.cell
return grad_nuc(cell, atmlst)
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def as_scanner(mf_grad):
'''Generating a nuclear gradients scanner/solver (for geometry optimizer).
The returned solver is a function. This function requires one argument
"cell" as input and returns energy and first order nuclear derivatives.
The solver will automatically use the results of last calculation as the
initial guess of the new calculation. All parameters assigned in the
nuc-grad object and SCF object (DIIS, conv_tol, max_memory etc) are
automatically applied in the solver.
Note scanner has side effects. It may change many underlying objects
(_scf, with_df, with_x2c, ...) during calculation.
'''
if isinstance(mf_grad, lib.GradScanner):
return mf_grad
logger.info(mf_grad, 'Create scanner for %s', mf_grad.__class__)
name = mf_grad.__class__.__name__ + SCF_GradScanner.__name_mixin__
return lib.set_class(SCF_GradScanner(mf_grad),
(SCF_GradScanner, mf_grad.__class__), name)
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class SCF_GradScanner(lib.GradScanner):
def __init__(self, g):
lib.GradScanner.__init__(self, g)
def __call__(self, cell_or_geom, **kwargs):
if isinstance(cell_or_geom, gto.Cell):
cell = cell_or_geom
else:
cell = self.cell.set_geom_(cell_or_geom, inplace=False)
mf_scanner = self.base
e_tot = mf_scanner(cell)
self.cell = cell
# If second integration grids are created for RKS and UKS
# gradients
if getattr(self, 'grids', None):
self.grids.reset(cell)
de = self.kernel(**kwargs)
return e_tot, de
[docs]
class Gradients(GradientsBase):
'''Non-relativistic restricted Hartree-Fock gradients'''
[docs]
def get_veff(self, dm=None, kpts=None):
if kpts is None: kpts = self.kpts
if dm is None: dm = self.base.make_rdm1()
return get_veff(self, dm, kpts)
[docs]
def make_rdm1e(self, mo_energy=None, mo_coeff=None, mo_occ=None):
if mo_energy is None: mo_energy = self.base.mo_energy
if mo_coeff is None: mo_coeff = self.base.mo_coeff
if mo_occ is None: mo_occ = self.base.mo_occ
return make_rdm1e(mo_energy, mo_coeff, mo_occ)
grad_elec = grad_elec
as_scanner = as_scanner
def _finalize(self):
if self.verbose >= logger.NOTE:
logger.note(self, '--------------- %s gradients ---------------',
self.base.__class__.__name__)
self._write(self.cell, self.de, self.atmlst)
logger.note(self, '----------------------------------------------')
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def kernel(self, mo_energy=None, mo_coeff=None, mo_occ=None, atmlst=None):
cput0 = (logger.process_clock(), logger.perf_counter())
if mo_energy is None: mo_energy = self.base.mo_energy
if mo_coeff is None: mo_coeff = self.base.mo_coeff
if mo_occ is None: mo_occ = self.base.mo_occ
if atmlst is None:
atmlst = self.atmlst
else:
self.atmlst = atmlst
if self.verbose >= logger.INFO:
self.dump_flags()
de = self.grad_elec(mo_energy, mo_coeff, mo_occ, atmlst)
self.de = de + self.grad_nuc(atmlst=atmlst)
logger.timer(self, 'SCF gradients', *cput0)
self._finalize()
return self.de
if __name__=='__main__':
from pyscf.pbc import scf
cell = gto.Cell()
cell.atom = '''
He 0.0 0.0 0.0
He 1.0 1.1 1.2
'''
cell.basis = 'gth-dzv'
cell.a = np.eye(3) * 3
cell.unit='bohr'
cell.pseudo='gth-pade'
cell.verbose=4
cell.build()
nmp = [1,1,3]
kpts = cell.make_kpts(nmp)
kmf = scf.KRHF(cell, kpts, exxdiv=None)
kmf.kernel()
mygrad = Gradients(kmf)
grad = mygrad.kernel()