def get_vxc_soc(ni, mol, grids, xc_code, dms, max_memory=2000, verbose=None): xctype = ni._xc_type(xc_code) make_rho, nset, nao = ni._gen_rho_evaluator(mol, dms, hermi=1) ngrids = len(grids.weights) BLKSIZE = numint.BLKSIZE blksize = min( int(max_memory / 12 * 1e6 / 8 / nao / BLKSIZE) * BLKSIZE, ngrids) shls_slice = (0, mol.nbas) ao_loc = mol.ao_loc_nr() vmat = numpy.zeros((2, 3, nao, nao)) if xctype == 'LDA': buf = numpy.empty((4, blksize, nao)) ao_deriv = 1 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory, blksize=blksize, buf=buf): rho_a = make_rho(0, ao[0], mask, 'LDA') rho_b = make_rho(1, ao[0], mask, 'LDA') vxc = ni.eval_xc(xc_code, (rho_a, rho_b), 1, deriv=1)[1] vrho = vxc[0] aow = numpy.einsum('xpi,p->xpi', ao[1:], weight * vrho[:, 0]) _cross3x3_(vmat[0], mol, aow, ao[1:], mask, shls_slice, ao_loc) aow = numpy.einsum('xpi,p->xpi', ao[1:], weight * vrho[:, 1]) _cross3x3_(vmat[1], mol, aow, ao[1:], mask, shls_slice, ao_loc) rho = vxc = vrho = aow = None elif xctype == 'GGA': buf = numpy.empty((10, blksize, nao)) ao_deriv = 2 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory, blksize=blksize, buf=buf): rho_a = make_rho(0, ao, mask, 'GGA') rho_b = make_rho(1, ao, mask, 'GGA') vxc = ni.eval_xc(xc_code, (rho_a, rho_b), 1, deriv=1)[1] wva, wvb = numint._uks_gga_wv0((rho_a, rho_b), vxc, weight) ip_ao = ao[1:4] ipip_ao = ao[4:] aow = rks_grad._make_dR_dao_w(ao, wva) _cross3x3_(vmat[0], mol, aow, ip_ao, mask, shls_slice, ao_loc) aow = rks_grad._make_dR_dao_w(ao, wvb) _cross3x3_(vmat[1], mol, aow, ip_ao, mask, shls_slice, ao_loc) rho = vxc = vrho = vsigma = wv = aow = None vmat = vmat - vmat.transpose(0, 1, 3, 2) else: raise NotImplementedError('meta-GGA') return vmat
def get_vxc_soc(ni, mol, grids, xc_code, dms, max_memory=2000, verbose=None): xctype = ni._xc_type(xc_code) make_rho, nset, nao = ni._gen_rho_evaluator(mol, dms, hermi=1) ngrids = len(grids.weights) BLKSIZE = numint.BLKSIZE blksize = min(int(max_memory/12*1e6/8/nao/BLKSIZE)*BLKSIZE, ngrids) shls_slice = (0, mol.nbas) ao_loc = mol.ao_loc_nr() vmat = numpy.zeros((2,3,nao,nao)) if xctype == 'LDA': buf = numpy.empty((4,blksize,nao)) ao_deriv = 1 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory, blksize=blksize, buf=buf): rho_a = make_rho(0, ao[0], mask, 'LDA') rho_b = make_rho(1, ao[0], mask, 'LDA') vxc = ni.eval_xc(xc_code, (rho_a, rho_b), 1, deriv=1)[1] vrho = vxc[0] aow = numpy.einsum('xpi,p->xpi', ao[1:], weight*vrho[:,0]) _cross3x3_(vmat[0], mol, aow, ao[1:], mask, shls_slice, ao_loc) aow = numpy.einsum('xpi,p->xpi', ao[1:], weight*vrho[:,1]) _cross3x3_(vmat[1], mol, aow, ao[1:], mask, shls_slice, ao_loc) rho = vxc = vrho = aow = None elif xctype == 'GGA': buf = numpy.empty((10,blksize,nao)) ao_deriv = 2 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory, blksize=blksize, buf=buf): rho_a = make_rho(0, ao, mask, 'GGA') rho_b = make_rho(1, ao, mask, 'GGA') vxc = ni.eval_xc(xc_code, (rho_a,rho_b), 1, deriv=1)[1] wva, wvb = numint._uks_gga_wv0((rho_a, rho_b), vxc, weight) ip_ao = ao[1:4] ipip_ao = ao[4:] aow = rks_grad._make_dR_dao_w(ao, wva) _cross3x3_(vmat[0], mol, aow, ip_ao, mask, shls_slice, ao_loc) aow = rks_grad._make_dR_dao_w(ao, wvb) _cross3x3_(vmat[1], mol, aow, ip_ao, mask, shls_slice, ao_loc) rho = vxc = vrho = vsigma = wv = aow = None vmat = vmat - vmat.transpose(0,1,3,2) else: raise NotImplementedError('meta-GGA') return vmat
def _get_vxc_deriv2(hessobj, mo_coeff, mo_occ, max_memory): mol = hessobj.mol mf = hessobj.base if hessobj.grids is not None: grids = hessobj.grids else: grids = mf.grids if grids.coords is None: grids.build(with_non0tab=True) nao, nmo = mo_coeff[0].shape ni = mf._numint xctype = ni._xc_type(mf.xc) aoslices = mol.aoslice_by_atom() shls_slice = (0, mol.nbas) ao_loc = mol.ao_loc_nr() dm0a, dm0b = mf.make_rdm1(mo_coeff, mo_occ) vmata = numpy.zeros((mol.natm,3,3,nao,nao)) vmatb = numpy.zeros((mol.natm,3,3,nao,nao)) ipipa = numpy.zeros((3,3,nao,nao)) ipipb = numpy.zeros((3,3,nao,nao)) if xctype == 'LDA': ao_deriv = 1 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory): rhoa = ni.eval_rho2(mol, ao[0], mo_coeff[0], mo_occ[0], mask, xctype) rhob = ni.eval_rho2(mol, ao[0], mo_coeff[1], mo_occ[1], mask, xctype) vxc, fxc = ni.eval_xc(mf.xc, (rhoa,rhob), 1, deriv=2)[1:3] vrho = vxc[0] u_u, u_d, d_d = fxc[0].T aow = numpy.einsum('xpi,p->xpi', ao[1:4], weight*vrho[:,0]) rks_hess._d1d2_dot_(ipipa, mol, aow, ao[1:4], mask, ao_loc, False) aow = numpy.einsum('xpi,p->xpi', ao[1:4], weight*vrho[:,1]) rks_hess._d1d2_dot_(ipipb, mol, aow, ao[1:4], mask, ao_loc, False) ao_dm0a = numint._dot_ao_dm(mol, ao[0], dm0a, mask, shls_slice, ao_loc) ao_dm0b = numint._dot_ao_dm(mol, ao[0], dm0b, mask, shls_slice, ao_loc) for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] # *2 for \nabla|ket> in rho1 rho1a = numpy.einsum('xpi,pi->xp', ao[1:,:,p0:p1], ao_dm0a[:,p0:p1]) * 2 rho1b = numpy.einsum('xpi,pi->xp', ao[1:,:,p0:p1], ao_dm0b[:,p0:p1]) * 2 wv = u_u * rho1a + u_d * rho1b wv *= weight # aow ~ rho1 ~ d/dR1 aow = numpy.einsum('pi,xp->xpi', ao[0], wv) rks_hess._d1d2_dot_(vmata[ia], mol, ao[1:4], aow, mask, ao_loc, False) wv = u_d * rho1a + d_d * rho1b wv *= weight aow = numpy.einsum('pi,xp->xpi', ao[0], wv) rks_hess._d1d2_dot_(vmatb[ia], mol, ao[1:4], aow, mask, ao_loc, False) ao_dm0a = ao_dm0b = aow = None for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] vmata[ia,:,:,:,p0:p1] += ipipa[:,:,:,p0:p1] vmatb[ia,:,:,:,p0:p1] += ipipb[:,:,:,p0:p1] elif xctype == 'GGA': ao_deriv = 2 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory): rhoa = ni.eval_rho2(mol, ao[:4], mo_coeff[0], mo_occ[0], mask, xctype) rhob = ni.eval_rho2(mol, ao[:4], mo_coeff[1], mo_occ[1], mask, xctype) vxc, fxc = ni.eval_xc(mf.xc, (rhoa,rhob), 1, deriv=2)[1:3] wva, wvb = numint._uks_gga_wv0((rhoa,rhob), vxc, weight) aow = rks_grad._make_dR_dao_w(ao, wva) rks_hess._d1d2_dot_(ipipa, mol, aow, ao[1:4], mask, ao_loc, False) aow = rks_grad._make_dR_dao_w(ao, wvb) rks_hess._d1d2_dot_(ipipb, mol, aow, ao[1:4], mask, ao_loc, False) ao_dm0a = [numint._dot_ao_dm(mol, ao[i], dm0a, mask, shls_slice, ao_loc) for i in range(4)] ao_dm0b = [numint._dot_ao_dm(mol, ao[i], dm0b, mask, shls_slice, ao_loc) for i in range(4)] for ia in range(mol.natm): wva = dR_rho1a = rks_hess._make_dR_rho1(ao, ao_dm0a, ia, aoslices) wvb = dR_rho1b = rks_hess._make_dR_rho1(ao, ao_dm0b, ia, aoslices) wva[0], wvb[0] = numint._uks_gga_wv1((rhoa,rhob), (dR_rho1a[0],dR_rho1b[0]), vxc, fxc, weight) wva[1], wvb[1] = numint._uks_gga_wv1((rhoa,rhob), (dR_rho1a[1],dR_rho1b[1]), vxc, fxc, weight) wva[2], wvb[2] = numint._uks_gga_wv1((rhoa,rhob), (dR_rho1a[2],dR_rho1b[2]), vxc, fxc, weight) aow = rks_grad._make_dR_dao_w(ao, wva[0]) rks_grad._d1_dot_(vmata[ia,0], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wva[1]) rks_grad._d1_dot_(vmata[ia,1], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wva[2]) rks_grad._d1_dot_(vmata[ia,2], mol, aow, ao[0], mask, ao_loc, True) aow = numpy.einsum('npi,Xnp->Xpi', ao[:4], wva) rks_hess._d1d2_dot_(vmata[ia], mol, ao[1:4], aow, mask, ao_loc, False) aow = rks_grad._make_dR_dao_w(ao, wvb[0]) rks_grad._d1_dot_(vmatb[ia,0], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wvb[1]) rks_grad._d1_dot_(vmatb[ia,1], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wvb[2]) rks_grad._d1_dot_(vmatb[ia,2], mol, aow, ao[0], mask, ao_loc, True) aow = numpy.einsum('npi,Xnp->Xpi', ao[:4], wvb) rks_hess._d1d2_dot_(vmatb[ia], mol, ao[1:4], aow, mask, ao_loc, False) ao_dm0a = ao_dm0b = aow = None for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] vmata[ia,:,:,:,p0:p1] += ipipa[:,:,:,p0:p1] vmata[ia,:,:,:,p0:p1] += ipipa[:,:,p0:p1].transpose(1,0,3,2) vmatb[ia,:,:,:,p0:p1] += ipipb[:,:,:,p0:p1] vmatb[ia,:,:,:,p0:p1] += ipipb[:,:,p0:p1].transpose(1,0,3,2) elif xctype == 'MGGA': raise NotImplementedError('meta-GGA') return vmata, vmatb
def _get_vxc_deriv2(hessobj, mo_coeff, mo_occ, max_memory): mol = hessobj.mol mf = hessobj.base if hessobj.grids is not None: grids = hessobj.grids else: grids = mf.grids if grids.coords is None: grids.build(with_non0tab=True) nao, nmo = mo_coeff[0].shape ni = mf._numint xctype = ni._xc_type(mf.xc) aoslices = mol.aoslice_by_atom() shls_slice = (0, mol.nbas) ao_loc = mol.ao_loc_nr() dm0a, dm0b = mf.make_rdm1(mo_coeff, mo_occ) vmata = numpy.zeros((mol.natm,3,3,nao,nao)) vmatb = numpy.zeros((mol.natm,3,3,nao,nao)) ipipa = numpy.zeros((3,3,nao,nao)) ipipb = numpy.zeros((3,3,nao,nao)) if xctype == 'LDA': ao_deriv = 1 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory): rhoa = ni.eval_rho2(mol, ao[0], mo_coeff[0], mo_occ[0], mask, xctype) rhob = ni.eval_rho2(mol, ao[0], mo_coeff[1], mo_occ[1], mask, xctype) vxc, fxc = ni.eval_xc(mf.xc, (rhoa,rhob), 1, deriv=2)[1:3] vrho = vxc[0] u_u, u_d, d_d = fxc[0].T aow = numpy.einsum('xpi,p->xpi', ao[1:4], weight*vrho[:,0]) rks_hess._d1d2_dot_(ipipa, mol, aow, ao[1:4], mask, ao_loc, False) aow = numpy.einsum('xpi,p->xpi', ao[1:4], weight*vrho[:,1]) rks_hess._d1d2_dot_(ipipb, mol, aow, ao[1:4], mask, ao_loc, False) ao_dm0a = numint._dot_ao_dm(mol, ao[0], dm0a, mask, shls_slice, ao_loc) ao_dm0b = numint._dot_ao_dm(mol, ao[0], dm0b, mask, shls_slice, ao_loc) for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] # *2 for \nabla|ket> in rho1 rho1a = numpy.einsum('xpi,pi->xp', ao[1:,:,p0:p1], ao_dm0a[:,p0:p1]) * 2 rho1b = numpy.einsum('xpi,pi->xp', ao[1:,:,p0:p1], ao_dm0b[:,p0:p1]) * 2 wv = u_u * rho1a + u_d * rho1b wv *= weight # aow ~ rho1 ~ d/dR1 aow = numpy.einsum('pi,xp->xpi', ao[0], wv) rks_hess._d1d2_dot_(vmata[ia], mol, ao[1:4], aow, mask, ao_loc, False) wv = u_d * rho1a + d_d * rho1b wv *= weight aow = numpy.einsum('pi,xp->xpi', ao[0], wv) rks_hess._d1d2_dot_(vmatb[ia], mol, ao[1:4], aow, mask, ao_loc, False) ao_dm0a = ao_dm0b = aow = None for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] vmata[ia,:,:,:,p0:p1] += ipipa[:,:,:,p0:p1] vmatb[ia,:,:,:,p0:p1] += ipipb[:,:,:,p0:p1] elif xctype == 'GGA': ao_deriv = 2 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory): rhoa = ni.eval_rho2(mol, ao[:4], mo_coeff[0], mo_occ[0], mask, xctype) rhob = ni.eval_rho2(mol, ao[:4], mo_coeff[1], mo_occ[1], mask, xctype) vxc, fxc = ni.eval_xc(mf.xc, (rhoa,rhob), 1, deriv=2)[1:3] wva, wvb = numint._uks_gga_wv0((rhoa,rhob), vxc, weight) aow = rks_grad._make_dR_dao_w(ao, wva) rks_hess._d1d2_dot_(ipipa, mol, aow, ao[1:4], mask, ao_loc, False) aow = rks_grad._make_dR_dao_w(ao, wvb) rks_hess._d1d2_dot_(ipipb, mol, aow, ao[1:4], mask, ao_loc, False) ao_dm0a = [numint._dot_ao_dm(mol, ao[i], dm0a, mask, shls_slice, ao_loc) for i in range(4)] ao_dm0b = [numint._dot_ao_dm(mol, ao[i], dm0b, mask, shls_slice, ao_loc) for i in range(4)] for ia in range(mol.natm): wva = dR_rho1a = rks_hess._make_dR_rho1(ao, ao_dm0a, ia, aoslices) wvb = dR_rho1b = rks_hess._make_dR_rho1(ao, ao_dm0b, ia, aoslices) wva[0], wvb[0] = numint._uks_gga_wv1((rhoa,rhob), (dR_rho1a[0],dR_rho1b[0]), vxc, fxc, weight) wva[1], wvb[1] = numint._uks_gga_wv1((rhoa,rhob), (dR_rho1a[1],dR_rho1b[1]), vxc, fxc, weight) wva[2], wvb[2] = numint._uks_gga_wv1((rhoa,rhob), (dR_rho1a[2],dR_rho1b[2]), vxc, fxc, weight) aow = rks_grad._make_dR_dao_w(ao, wva[0]) rks_grad._d1_dot_(vmata[ia,0], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wva[1]) rks_grad._d1_dot_(vmata[ia,1], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wva[2]) rks_grad._d1_dot_(vmata[ia,2], mol, aow, ao[0], mask, ao_loc, True) aow = numpy.einsum('npi,Xnp->Xpi', ao[:4], wva) rks_hess._d1d2_dot_(vmata[ia], mol, ao[1:4], aow, mask, ao_loc, False) aow = rks_grad._make_dR_dao_w(ao, wvb[0]) rks_grad._d1_dot_(vmatb[ia,0], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wvb[1]) rks_grad._d1_dot_(vmatb[ia,1], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wvb[2]) rks_grad._d1_dot_(vmatb[ia,2], mol, aow, ao[0], mask, ao_loc, True) aow = numpy.einsum('npi,Xnp->Xpi', ao[:4], wvb) rks_hess._d1d2_dot_(vmatb[ia], mol, ao[1:4], aow, mask, ao_loc, False) ao_dm0a = ao_dm0b = aow = None for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] vmata[ia,:,:,:,p0:p1] += ipipa[:,:,:,p0:p1] vmata[ia,:,:,:,p0:p1] += ipipa[:,:,p0:p1].transpose(1,0,3,2) vmatb[ia,:,:,:,p0:p1] += ipipb[:,:,:,p0:p1] vmatb[ia,:,:,:,p0:p1] += ipipb[:,:,p0:p1].transpose(1,0,3,2) elif xctype == 'MGGA': raise NotImplementedError('meta-GGA') return vmata, vmatb
def _get_vxc_deriv2(hessobj, mo_coeff, mo_occ, max_memory): mol = hessobj.mol mf = hessobj.base if hessobj.grids is not None: grids = hessobj.grids else: grids = mf.grids if grids.coords is None: grids.build(with_non0tab=True) nao, nmo = mo_coeff.shape ni = mf._numint xctype = ni._xc_type(mf.xc) aoslices = mol.aoslice_by_atom() shls_slice = (0, mol.nbas) ao_loc = mol.ao_loc_nr() dm0 = mf.make_rdm1(mo_coeff, mo_occ) vmat = numpy.zeros((mol.natm, 3, 3, nao, nao)) ipip = numpy.zeros((3, 3, nao, nao)) if xctype == 'LDA': ao_deriv = 1 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory): rho = ni.eval_rho2(mol, ao[0], mo_coeff, mo_occ, mask, 'LDA') vxc, fxc = ni.eval_xc(mf.xc, rho, 0, deriv=2)[1:3] vrho = vxc[0] frr = fxc[0] aow = numpy.einsum('xpi,p->xpi', ao[1:4], weight * vrho) _d1d2_dot_(ipip, mol, aow, ao[1:4], mask, ao_loc, False) ao_dm0 = numint._dot_ao_dm(mol, ao[0], dm0, mask, shls_slice, ao_loc) for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] # *2 for \nabla|ket> in rho1 rho1 = numpy.einsum('xpi,pi->xp', ao[1:, :, p0:p1], ao_dm0[:, p0:p1]) * 2 # aow ~ rho1 ~ d/dR1 aow = numpy.einsum('pi,xp->xpi', ao[0], weight * frr * rho1) _d1d2_dot_(vmat[ia], mol, ao[1:4], aow, mask, ao_loc, False) ao_dm0 = aow = None for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] vmat[ia, :, :, :, p0:p1] += ipip[:, :, :, p0:p1] elif xctype == 'GGA': ao_deriv = 2 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory): rho = ni.eval_rho2(mol, ao[:4], mo_coeff, mo_occ, mask, 'GGA') vxc, fxc = ni.eval_xc(mf.xc, rho, 0, deriv=2)[1:3] wv = numint._rks_gga_wv0(rho, vxc, weight) aow = rks_grad._make_dR_dao_w(ao, wv) _d1d2_dot_(ipip, mol, aow, ao[1:4], mask, ao_loc, False) ao_dm0 = [ numint._dot_ao_dm(mol, ao[i], dm0, mask, shls_slice, ao_loc) for i in range(4) ] for ia in range(mol.natm): wv = dR_rho1 = _make_dR_rho1(ao, ao_dm0, ia, aoslices) wv[0] = numint._rks_gga_wv1(rho, dR_rho1[0], vxc, fxc, weight) wv[1] = numint._rks_gga_wv1(rho, dR_rho1[1], vxc, fxc, weight) wv[2] = numint._rks_gga_wv1(rho, dR_rho1[2], vxc, fxc, weight) aow = rks_grad._make_dR_dao_w(ao, wv[0]) rks_grad._d1_dot_(vmat[ia, 0], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wv[1]) rks_grad._d1_dot_(vmat[ia, 1], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wv[2]) rks_grad._d1_dot_(vmat[ia, 2], mol, aow, ao[0], mask, ao_loc, True) aow = numpy.einsum('npi,Xnp->Xpi', ao[:4], wv) _d1d2_dot_(vmat[ia], mol, ao[1:4], aow, mask, ao_loc, False) ao_dm0 = aow = None for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] vmat[ia, :, :, :, p0:p1] += ipip[:, :, :, p0:p1] vmat[ia, :, :, :, p0:p1] += ipip[:, :, p0:p1].transpose(1, 0, 3, 2) elif xctype == 'MGGA': raise NotImplementedError('meta-GGA') return vmat
def _get_vxc_deriv2(hessobj, mo_coeff, mo_occ, max_memory): mol = hessobj.mol mf = hessobj.base if hessobj.grids is not None: grids = hessobj.grids else: grids = mf.grids if grids.coords is None: grids.build(with_non0tab=True) nao, nmo = mo_coeff.shape ni = mf._numint xctype = ni._xc_type(mf.xc) aoslices = mol.aoslice_by_atom() shls_slice = (0, mol.nbas) ao_loc = mol.ao_loc_nr() dm0 = mf.make_rdm1(mo_coeff, mo_occ) vmat = numpy.zeros((mol.natm,3,3,nao,nao)) ipip = numpy.zeros((3,3,nao,nao)) if xctype == 'LDA': ao_deriv = 1 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory): rho = ni.eval_rho2(mol, ao[0], mo_coeff, mo_occ, mask, 'LDA') vxc, fxc = ni.eval_xc(mf.xc, rho, 0, deriv=2)[1:3] vrho = vxc[0] frr = fxc[0] aow = numpy.einsum('xpi,p->xpi', ao[1:4], weight*vrho) _d1d2_dot_(ipip, mol, aow, ao[1:4], mask, ao_loc, False) ao_dm0 = numint._dot_ao_dm(mol, ao[0], dm0, mask, shls_slice, ao_loc) for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] # *2 for \nabla|ket> in rho1 rho1 = numpy.einsum('xpi,pi->xp', ao[1:,:,p0:p1], ao_dm0[:,p0:p1]) * 2 # aow ~ rho1 ~ d/dR1 aow = numpy.einsum('pi,xp->xpi', ao[0], weight*frr*rho1) _d1d2_dot_(vmat[ia], mol, ao[1:4], aow, mask, ao_loc, False) ao_dm0 = aow = None for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] vmat[ia,:,:,:,p0:p1] += ipip[:,:,:,p0:p1] elif xctype == 'GGA': ao_deriv = 2 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory): rho = ni.eval_rho2(mol, ao[:4], mo_coeff, mo_occ, mask, 'GGA') vxc, fxc = ni.eval_xc(mf.xc, rho, 0, deriv=2)[1:3] wv = numint._rks_gga_wv0(rho, vxc, weight) aow = rks_grad._make_dR_dao_w(ao, wv) _d1d2_dot_(ipip, mol, aow, ao[1:4], mask, ao_loc, False) ao_dm0 = [numint._dot_ao_dm(mol, ao[i], dm0, mask, shls_slice, ao_loc) for i in range(4)] for ia in range(mol.natm): wv = dR_rho1 = _make_dR_rho1(ao, ao_dm0, ia, aoslices) wv[0] = numint._rks_gga_wv1(rho, dR_rho1[0], vxc, fxc, weight) wv[1] = numint._rks_gga_wv1(rho, dR_rho1[1], vxc, fxc, weight) wv[2] = numint._rks_gga_wv1(rho, dR_rho1[2], vxc, fxc, weight) aow = rks_grad._make_dR_dao_w(ao, wv[0]) rks_grad._d1_dot_(vmat[ia,0], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wv[1]) rks_grad._d1_dot_(vmat[ia,1], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wv[2]) rks_grad._d1_dot_(vmat[ia,2], mol, aow, ao[0], mask, ao_loc, True) aow = numpy.einsum('npi,Xnp->Xpi', ao[:4], wv) _d1d2_dot_(vmat[ia], mol, ao[1:4], aow, mask, ao_loc, False) ao_dm0 = aow = None for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] vmat[ia,:,:,:,p0:p1] += ipip[:,:,:,p0:p1] vmat[ia,:,:,:,p0:p1] += ipip[:,:,p0:p1].transpose(1,0,3,2) elif xctype == 'MGGA': raise NotImplementedError('meta-GGA') return vmat
def _get_vxc_deriv2(hessobj, mo_coeff, mo_occ, max_memory): mol = hessobj.mol mf = hessobj.base if hessobj.grids is not None: grids = hessobj.grids else: grids = mf.grids if grids.coords is None: grids.build(with_non0tab=True) nao, nmo = mo_coeff.shape ni = mf._numint xctype = ni._xc_type(mf.xc) aoslices = mol.aoslice_by_atom() shls_slice = (0, mol.nbas) ao_loc = mol.ao_loc_nr() dm0 = mf.make_rdm1(mo_coeff, mo_occ) vmat = numpy.zeros((mol.natm, 3, 3, nao, nao)) ipip = numpy.zeros((3, 3, nao, nao)) if xctype == 'LDA': ao_deriv = 1 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory): rho = ni.eval_rho2(mol, ao[0], mo_coeff, mo_occ, mask, xctype) vxc, fxc = ni.eval_xc(mf.xc, rho, 0, deriv=2)[1:3] vrho = vxc[0] frr = fxc[0] wv = weight * vrho aow = [numint._scale_ao(ao[i], wv) for i in range(1, 4)] _d1d2_dot_(ipip, mol, aow, ao[1:4], mask, ao_loc, False) ao_dm0 = numint._dot_ao_dm(mol, ao[0], dm0, mask, shls_slice, ao_loc) for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] # *2 for \nabla|ket> in rho1 rho1 = numpy.einsum('xpi,pi->xp', ao[1:, :, p0:p1], ao_dm0[:, p0:p1]) * 2 # aow ~ rho1 ~ d/dR1 wv = weight * frr * rho1 aow = [numint._scale_ao(ao[0], wv[i]) for i in range(3)] _d1d2_dot_(vmat[ia], mol, ao[1:4], aow, mask, ao_loc, False) ao_dm0 = aow = None for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] vmat[ia, :, :, :, p0:p1] += ipip[:, :, :, p0:p1] elif xctype == 'GGA': ao_deriv = 2 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory): rho = ni.eval_rho2(mol, ao[:4], mo_coeff, mo_occ, mask, xctype) vxc, fxc = ni.eval_xc(mf.xc, rho, 0, deriv=2)[1:3] wv = numint._rks_gga_wv0(rho, vxc, weight) aow = rks_grad._make_dR_dao_w(ao, wv) _d1d2_dot_(ipip, mol, aow, ao[1:4], mask, ao_loc, False) ao_dm0 = [ numint._dot_ao_dm(mol, ao[i], dm0, mask, shls_slice, ao_loc) for i in range(4) ] for ia in range(mol.natm): wv = dR_rho1 = _make_dR_rho1(ao, ao_dm0, ia, aoslices) for i in range(3): wv[i] = numint._rks_gga_wv1(rho, dR_rho1[i], vxc, fxc, weight) aow = rks_grad._make_dR_dao_w(ao, wv[i]) rks_grad._d1_dot_(vmat[ia, i], mol, aow, ao[0], mask, ao_loc, True) aow = [numint._scale_ao(ao[:4], wv[i, :4]) for i in range(3)] _d1d2_dot_(vmat[ia], mol, ao[1:4], aow, mask, ao_loc, False) ao_dm0 = aow = None for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] vmat[ia, :, :, :, p0:p1] += ipip[:, :, :, p0:p1] vmat[ia, :, :, :, p0:p1] += ipip[:, :, p0:p1].transpose(1, 0, 3, 2) elif xctype == 'MGGA': XX, XY, XZ = 4, 5, 6 YX, YY, YZ = 5, 7, 8 ZX, ZY, ZZ = 6, 8, 9 ao_deriv = 2 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory): rho = ni.eval_rho2(mol, ao[:10], mo_coeff, mo_occ, mask, xctype) vxc, fxc = ni.eval_xc(mf.xc, rho, 0, deriv=2)[1:3] wv = numint._rks_mgga_wv0(rho, vxc, weight) aow = rks_grad._make_dR_dao_w(ao, wv) _d1d2_dot_(ipip, mol, aow, ao[1:4], mask, ao_loc, False) aow = [numint._scale_ao(ao[i], wv[5]) for i in range(4, 10)] _d1d2_dot_(ipip, mol, [aow[0], aow[1], aow[2]], [ao[XX], ao[XY], ao[XZ]], mask, ao_loc, False) _d1d2_dot_(ipip, mol, [aow[1], aow[3], aow[4]], [ao[YX], ao[YY], ao[YZ]], mask, ao_loc, False) _d1d2_dot_(ipip, mol, [aow[2], aow[4], aow[5]], [ao[ZX], ao[ZY], ao[ZZ]], mask, ao_loc, False) ao_dm0 = [ numint._dot_ao_dm(mol, ao[i], dm0, mask, shls_slice, ao_loc) for i in range(4) ] for ia in range(mol.natm): wv = dR_rho1 = _make_dR_rho1(ao, ao_dm0, ia, aoslices, xctype) for i in range(3): wv[i] = numint._rks_mgga_wv1(rho, dR_rho1[i], vxc, fxc, weight) aow = rks_grad._make_dR_dao_w(ao, wv[i]) rks_grad._d1_dot_(vmat[ia, i], mol, aow, ao[0], mask, ao_loc, True) aow = [numint._scale_ao(ao[:4], wv[i, :4]) for i in range(3)] _d1d2_dot_(vmat[ia], mol, ao[1:4], aow, mask, ao_loc, False) # *2 because wv[5] is scaled by 0.5 in _rks_mgga_wv1 wv[:, 5] *= 2 aow = [numint._scale_ao(ao[1], wv[i, 5]) for i in range(3)] _d1d2_dot_(vmat[ia], mol, [ao[XX], ao[XY], ao[XZ]], aow, mask, ao_loc, False) aow = [numint._scale_ao(ao[2], wv[i, 5]) for i in range(3)] _d1d2_dot_(vmat[ia], mol, [ao[YX], ao[YY], ao[YZ]], aow, mask, ao_loc, False) aow = [numint._scale_ao(ao[3], wv[i, 5]) for i in range(3)] _d1d2_dot_(vmat[ia], mol, [ao[ZX], ao[ZY], ao[ZZ]], aow, mask, ao_loc, False) for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] vmat[ia, :, :, :, p0:p1] += ipip[:, :, :, p0:p1] vmat[ia, :, :, :, p0:p1] += ipip[:, :, p0:p1].transpose(1, 0, 3, 2) return vmat
def _get_vxc_deriv2(hessobj, mo_coeff, mo_occ, max_memory): mol = hessobj.mol mf = hessobj.base if hessobj.grids is not None: grids = hessobj.grids else: grids = mf.grids if grids.coords is None: grids.build(with_non0tab=True) nao, nmo = mo_coeff[0].shape ni = mf._numint xctype = ni._xc_type(mf.xc) aoslices = mol.aoslice_by_atom() shls_slice = (0, mol.nbas) ao_loc = mol.ao_loc_nr() dm0a, dm0b = mf.make_rdm1(mo_coeff, mo_occ) vmata = numpy.zeros((mol.natm, 3, 3, nao, nao)) vmatb = numpy.zeros((mol.natm, 3, 3, nao, nao)) ipipa = numpy.zeros((3, 3, nao, nao)) ipipb = numpy.zeros((3, 3, nao, nao)) if xctype == 'LDA': ao_deriv = 1 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory): rhoa = ni.eval_rho2(mol, ao[0], mo_coeff[0], mo_occ[0], mask, xctype) rhob = ni.eval_rho2(mol, ao[0], mo_coeff[1], mo_occ[1], mask, xctype) vxc, fxc = ni.eval_xc(mf.xc, (rhoa, rhob), 1, deriv=2)[1:3] vrho = vxc[0] u_u, u_d, d_d = fxc[0].T aow = numpy.einsum('xpi,p->xpi', ao[1:4], weight * vrho[:, 0]) rks_hess._d1d2_dot_(ipipa, mol, aow, ao[1:4], mask, ao_loc, False) aow = numpy.einsum('xpi,p->xpi', ao[1:4], weight * vrho[:, 1]) rks_hess._d1d2_dot_(ipipb, mol, aow, ao[1:4], mask, ao_loc, False) ao_dm0a = numint._dot_ao_dm(mol, ao[0], dm0a, mask, shls_slice, ao_loc) ao_dm0b = numint._dot_ao_dm(mol, ao[0], dm0b, mask, shls_slice, ao_loc) for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] # *2 for \nabla|ket> in rho1 rho1a = numpy.einsum('xpi,pi->xp', ao[1:, :, p0:p1], ao_dm0a[:, p0:p1]) * 2 rho1b = numpy.einsum('xpi,pi->xp', ao[1:, :, p0:p1], ao_dm0b[:, p0:p1]) * 2 wv = u_u * rho1a + u_d * rho1b wv *= weight # aow ~ rho1 ~ d/dR1 aow = numpy.einsum('pi,xp->xpi', ao[0], wv) rks_hess._d1d2_dot_(vmata[ia], mol, ao[1:4], aow, mask, ao_loc, False) wv = u_d * rho1a + d_d * rho1b wv *= weight aow = numpy.einsum('pi,xp->xpi', ao[0], wv) rks_hess._d1d2_dot_(vmatb[ia], mol, ao[1:4], aow, mask, ao_loc, False) ao_dm0a = ao_dm0b = aow = None for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] vmata[ia, :, :, :, p0:p1] += ipipa[:, :, :, p0:p1] vmatb[ia, :, :, :, p0:p1] += ipipb[:, :, :, p0:p1] elif xctype == 'GGA': ao_deriv = 2 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory): rhoa = ni.eval_rho2(mol, ao[:4], mo_coeff[0], mo_occ[0], mask, xctype) rhob = ni.eval_rho2(mol, ao[:4], mo_coeff[1], mo_occ[1], mask, xctype) vxc, fxc = ni.eval_xc(mf.xc, (rhoa, rhob), 1, deriv=2)[1:3] wva, wvb = numint._uks_gga_wv0((rhoa, rhob), vxc, weight) aow = rks_grad._make_dR_dao_w(ao, wva) rks_hess._d1d2_dot_(ipipa, mol, aow, ao[1:4], mask, ao_loc, False) aow = rks_grad._make_dR_dao_w(ao, wvb) rks_hess._d1d2_dot_(ipipb, mol, aow, ao[1:4], mask, ao_loc, False) ao_dm0a = [ numint._dot_ao_dm(mol, ao[i], dm0a, mask, shls_slice, ao_loc) for i in range(4) ] ao_dm0b = [ numint._dot_ao_dm(mol, ao[i], dm0b, mask, shls_slice, ao_loc) for i in range(4) ] for ia in range(mol.natm): wva = dR_rho1a = rks_hess._make_dR_rho1( ao, ao_dm0a, ia, aoslices) wvb = dR_rho1b = rks_hess._make_dR_rho1( ao, ao_dm0b, ia, aoslices) wva[0], wvb[0] = numint._uks_gga_wv1( (rhoa, rhob), (dR_rho1a[0], dR_rho1b[0]), vxc, fxc, weight) wva[1], wvb[1] = numint._uks_gga_wv1( (rhoa, rhob), (dR_rho1a[1], dR_rho1b[1]), vxc, fxc, weight) wva[2], wvb[2] = numint._uks_gga_wv1( (rhoa, rhob), (dR_rho1a[2], dR_rho1b[2]), vxc, fxc, weight) aow = rks_grad._make_dR_dao_w(ao, wva[0]) rks_grad._d1_dot_(vmata[ia, 0], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wva[1]) rks_grad._d1_dot_(vmata[ia, 1], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wva[2]) rks_grad._d1_dot_(vmata[ia, 2], mol, aow, ao[0], mask, ao_loc, True) aow = [numint._scale_ao(ao[:4], wva[i, :4]) for i in range(3)] rks_hess._d1d2_dot_(vmata[ia], mol, ao[1:4], aow, mask, ao_loc, False) aow = rks_grad._make_dR_dao_w(ao, wvb[0]) rks_grad._d1_dot_(vmatb[ia, 0], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wvb[1]) rks_grad._d1_dot_(vmatb[ia, 1], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wvb[2]) rks_grad._d1_dot_(vmatb[ia, 2], mol, aow, ao[0], mask, ao_loc, True) aow = [numint._scale_ao(ao[:4], wvb[i, :4]) for i in range(3)] rks_hess._d1d2_dot_(vmatb[ia], mol, ao[1:4], aow, mask, ao_loc, False) ao_dm0a = ao_dm0b = aow = None for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] vmata[ia, :, :, :, p0:p1] += ipipa[:, :, :, p0:p1] vmata[ia, :, :, :, p0:p1] += ipipa[:, :, p0:p1].transpose(1, 0, 3, 2) vmatb[ia, :, :, :, p0:p1] += ipipb[:, :, :, p0:p1] vmatb[ia, :, :, :, p0:p1] += ipipb[:, :, p0:p1].transpose(1, 0, 3, 2) elif xctype == 'MGGA': XX, XY, XZ = 4, 5, 6 YX, YY, YZ = 5, 7, 8 ZX, ZY, ZZ = 6, 8, 9 ao_deriv = 2 for ao, mask, weight, coords \ in ni.block_loop(mol, grids, nao, ao_deriv, max_memory): rhoa = ni.eval_rho2(mol, ao[:10], mo_coeff[0], mo_occ[0], mask, xctype) rhob = ni.eval_rho2(mol, ao[:10], mo_coeff[1], mo_occ[1], mask, xctype) vxc, fxc = ni.eval_xc(mf.xc, (rhoa, rhob), 1, deriv=2)[1:3] wva, wvb = numint._uks_mgga_wv0((rhoa, rhob), vxc, weight) aow = rks_grad._make_dR_dao_w(ao, wva) rks_hess._d1d2_dot_(ipipa, mol, aow, ao[1:4], mask, ao_loc, False) aow = rks_grad._make_dR_dao_w(ao, wvb) rks_hess._d1d2_dot_(ipipb, mol, aow, ao[1:4], mask, ao_loc, False) aow = [numint._scale_ao(ao[i], wva[5]) for i in range(4, 10)] rks_hess._d1d2_dot_(ipipa, mol, [aow[0], aow[1], aow[2]], [ao[XX], ao[XY], ao[XZ]], mask, ao_loc, False) rks_hess._d1d2_dot_(ipipa, mol, [aow[1], aow[3], aow[4]], [ao[YX], ao[YY], ao[YZ]], mask, ao_loc, False) rks_hess._d1d2_dot_(ipipa, mol, [aow[2], aow[4], aow[5]], [ao[ZX], ao[ZY], ao[ZZ]], mask, ao_loc, False) aow = [numint._scale_ao(ao[i], wvb[5]) for i in range(4, 10)] rks_hess._d1d2_dot_(ipipb, mol, [aow[0], aow[1], aow[2]], [ao[XX], ao[XY], ao[XZ]], mask, ao_loc, False) rks_hess._d1d2_dot_(ipipb, mol, [aow[1], aow[3], aow[4]], [ao[YX], ao[YY], ao[YZ]], mask, ao_loc, False) rks_hess._d1d2_dot_(ipipb, mol, [aow[2], aow[4], aow[5]], [ao[ZX], ao[ZY], ao[ZZ]], mask, ao_loc, False) ao_dm0a = [ numint._dot_ao_dm(mol, ao[i], dm0a, mask, shls_slice, ao_loc) for i in range(4) ] ao_dm0b = [ numint._dot_ao_dm(mol, ao[i], dm0b, mask, shls_slice, ao_loc) for i in range(4) ] for ia in range(mol.natm): wva = dR_rho1a = rks_hess._make_dR_rho1( ao, ao_dm0a, ia, aoslices, xctype) wvb = dR_rho1b = rks_hess._make_dR_rho1( ao, ao_dm0b, ia, aoslices, xctype) wva[0], wvb[0] = numint._uks_mgga_wv1( (rhoa, rhob), (dR_rho1a[0], dR_rho1b[0]), vxc, fxc, weight) wva[1], wvb[1] = numint._uks_mgga_wv1( (rhoa, rhob), (dR_rho1a[1], dR_rho1b[1]), vxc, fxc, weight) wva[2], wvb[2] = numint._uks_mgga_wv1( (rhoa, rhob), (dR_rho1a[2], dR_rho1b[2]), vxc, fxc, weight) aow = rks_grad._make_dR_dao_w(ao, wva[0]) rks_grad._d1_dot_(vmata[ia, 0], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wva[1]) rks_grad._d1_dot_(vmata[ia, 1], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wva[2]) rks_grad._d1_dot_(vmata[ia, 2], mol, aow, ao[0], mask, ao_loc, True) aow = [numint._scale_ao(ao[:4], wva[i, :4]) for i in range(3)] rks_hess._d1d2_dot_(vmata[ia], mol, ao[1:4], aow, mask, ao_loc, False) aow = rks_grad._make_dR_dao_w(ao, wvb[0]) rks_grad._d1_dot_(vmatb[ia, 0], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wvb[1]) rks_grad._d1_dot_(vmatb[ia, 1], mol, aow, ao[0], mask, ao_loc, True) aow = rks_grad._make_dR_dao_w(ao, wvb[2]) rks_grad._d1_dot_(vmatb[ia, 2], mol, aow, ao[0], mask, ao_loc, True) aow = [numint._scale_ao(ao[:4], wvb[i, :4]) for i in range(3)] rks_hess._d1d2_dot_(vmatb[ia], mol, ao[1:4], aow, mask, ao_loc, False) # *2 because wv[5] is scaled by 0.5 in _rks_mgga_wv1 wv = wva[:, 5] * 2 aow = [numint._scale_ao(ao[1], wv[i]) for i in range(3)] rks_hess._d1d2_dot_(vmata[ia], mol, [ao[XX], ao[XY], ao[XZ]], aow, mask, ao_loc, False) aow = [numint._scale_ao(ao[2], wv[i]) for i in range(3)] rks_hess._d1d2_dot_(vmata[ia], mol, [ao[YX], ao[YY], ao[YZ]], aow, mask, ao_loc, False) aow = [numint._scale_ao(ao[3], wv[i]) for i in range(3)] rks_hess._d1d2_dot_(vmata[ia], mol, [ao[ZX], ao[ZY], ao[ZZ]], aow, mask, ao_loc, False) wv = wvb[:, 5] * 2 aow = [numint._scale_ao(ao[1], wv[i]) for i in range(3)] rks_hess._d1d2_dot_(vmatb[ia], mol, [ao[XX], ao[XY], ao[XZ]], aow, mask, ao_loc, False) aow = [numint._scale_ao(ao[2], wv[i]) for i in range(3)] rks_hess._d1d2_dot_(vmatb[ia], mol, [ao[YX], ao[YY], ao[YZ]], aow, mask, ao_loc, False) aow = [numint._scale_ao(ao[3], wv[i]) for i in range(3)] rks_hess._d1d2_dot_(vmatb[ia], mol, [ao[ZX], ao[ZY], ao[ZZ]], aow, mask, ao_loc, False) for ia in range(mol.natm): p0, p1 = aoslices[ia][2:] vmata[ia, :, :, :, p0:p1] += ipipa[:, :, :, p0:p1] vmata[ia, :, :, :, p0:p1] += ipipa[:, :, p0:p1].transpose(1, 0, 3, 2) vmatb[ia, :, :, :, p0:p1] += ipipb[:, :, :, p0:p1] vmatb[ia, :, :, :, p0:p1] += ipipb[:, :, p0:p1].transpose(1, 0, 3, 2) return vmata, vmatb