def calculate_exx_integrals(self):
# Find core states:
core = []
lmax = 0
for l, ch in enumerate(self.aea.channels):
for n, phi_g in enumerate(ch.phi_ng):
if l >= len(self.waves_l) or (l < len(self.waves_l) and n + l + 1 not in self.waves_l[l].n_n):
core.append((l, phi_g))
if l > lmax:
lmax = l
lmax = max(lmax, len(self.waves_l) - 1)
G_LLL = make_gaunt(lmax)
# Calculate core contribution to EXX energy:
self.exxcc = 0.0
j1 = 0
for l1, phi1_g in core:
f = 1.0
for l2, phi2_g in core[j1:]:
n_g = phi1_g * phi2_g
for l in range((l1 + l2) % 2, l1 + l2 + 1, 2):
G = (G_LLL[l1 ** 2 : (l1 + 1) ** 2, l2 ** 2 : (l2 + 1) ** 2, l ** 2 : (l + 1) ** 2] ** 2).sum()
vr_g = self.rgd.poisson(n_g, l)
e = f * self.rgd.integrate(vr_g * n_g, -1) / 4 / pi
self.exxcc -= e * G
f = 2.0
j1 += 1
self.log("EXX (core-core):", self.exxcc, "Hartree")
# Calculate core-valence contribution to EXX energy:
nj = sum(len(waves) for waves in self.waves_l)
ni = sum(len(waves) * (2 * l + 1) for l, waves in enumerate(self.waves_l))
self.exxcv_ii = np.zeros((ni, ni))
i1 = 0
for l1, waves1 in enumerate(self.waves_l):
for phi1_g in waves1.phi_ng:
i2 = 0
for l2, waves2 in enumerate(self.waves_l):
for phi2_g in waves2.phi_ng:
X_mm = self.exxcv_ii[i1 : i1 + 2 * l1 + 1, i2 : i2 + 2 * l2 + 1]
if (l1 + l2) % 2 == 0:
for lc, phi_g in core:
n_g = phi1_g * phi_g
for l in range((l1 + lc) % 2, max(l1, l2) + lc + 1, 2):
vr_g = self.rgd.poisson(phi2_g * phi_g, l)
e = self.rgd.integrate(vr_g * n_g, -1) / (4 * pi)
for mc in range(2 * lc + 1):
for m in range(2 * l + 1):
G_L = G_LLL[:, lc ** 2 + mc, l ** 2 + m]
X_mm += (
np.outer(G_L[l1 ** 2 : (l1 + 1) ** 2], G_L[l2 ** 2 : (l2 + 1) ** 2]) * e
)
i2 += 2 * l2 + 1
i1 += 2 * l1 + 1
def calculate_exx(self, s=None):
if s is None:
self.exx = sum(self.calculate_exx(s)
for s in range(self.nspins)) / self.nspins
return self.exx
states = []
lmax = 0
for ch in self.channels:
l = ch.l
for n, phi_g in enumerate(ch.phi_ng):
f = ch.f_n[n]
if f > 0 and ch.s == s:
states.append((l, f * self.nspins / 2.0 / (2 * l + 1),
phi_g))
if l > lmax:
lmax = l
G_LLL = make_gaunt(lmax)
exx = 0.0
j1 = 0
for l1, f1, phi1_g in states:
f = 1.0
for l2, f2, phi2_g in states[j1:]:
n_g = phi1_g * phi2_g
for l in range((l1 + l2) % 2, l1 + l2 + 1, 2):
G = (G_LLL[l1**2:(l1 + 1)**2,
l2**2:(l2 + 1)**2,
l**2:(l + 1)**2]**2).sum()
vr_g = self.rgd.poisson(n_g, l)
e = f * self.rgd.integrate(vr_g * n_g, -1) / 4 / pi
exx -= e * G * f1 * f2
f = 2.0
j1 += 1
return exx
def calculate_exx(self, s=None):
if s is None:
self.exx = sum(self.calculate_exx(s)
for s in range(self.nspins)) / self.nspins
return self.exx
states = []
lmax = 0
for ch in self.channels:
l = ch.l
for n, phi_g in enumerate(ch.phi_ng):
f = ch.f_n[n]
if f > 0 and ch.s == s:
states.append(
(l, f * self.nspins / 2.0 / (2 * l + 1), phi_g))
if l > lmax:
lmax = l
G_LLL = make_gaunt(lmax)
exx = 0.0
j1 = 0
for l1, f1, phi1_g in states:
f = 1.0
for l2, f2, phi2_g in states[j1:]:
n_g = phi1_g * phi2_g
for l in range((l1 + l2) % 2, l1 + l2 + 1, 2):
G = (G_LLL[l1**2:(l1 + 1)**2, l2**2:(l2 + 1)**2,
l**2:(l + 1)**2]**2).sum()
vr_g = self.rgd.poisson(n_g, l)
e = f * self.rgd.integrate(vr_g * n_g, -1) / 4 / pi
exx -= e * G * f1 * f2
f = 2.0
j1 += 1
return exx
def constructX(gen):
"""Construct the X_p^a matrix for the given atom.
The X_p^a matrix describes the valence-core interactions of the
partial waves.
"""
# initialize attributes
uv_j = gen.vu_j # soft valence states * r:
lv_j = gen.vl_j # their repective l quantum numbers
Nvi = 0
for l in lv_j:
Nvi += 2 * l + 1 # total number of valence states (including m)
# number of core and valence orbitals (j only, i.e. not m-number)
Njcore = gen.njcore
Njval = len(lv_j)
# core states * r:
uc_j = gen.u_j[:Njcore]
r, dr, N, beta = gen.r, gen.dr, gen.N, gen.beta
# potential times radius
vr = np.zeros(N)
# initialize X_ii matrix
X_ii = np.zeros((Nvi, Nvi))
# make gaunt coeff. list
lmax = max(gen.l_j[:Njcore] + gen.vl_j)
gaunt = make_gaunt(lmax=lmax)
# sum over core states
for jc in range(Njcore):
lc = gen.l_j[jc]
# sum over first valence state index
i1 = 0
for jv1 in range(Njval):
lv1 = lv_j[jv1]
# electron density 1 times radius times length element
n1c = uv_j[jv1] * uc_j[jc] * dr
n1c[1:] /= r[1:]
# sum over second valence state index
i2 = 0
for jv2 in range(Njval):
lv2 = lv_j[jv2]
# electron density 2
n2c = uv_j[jv2] * uc_j[jc] * dr
n2c[1:] /= r[1:]
# sum expansion in angular momenta
for l in range(min(lv1, lv2) + lc + 1):
# Int density * potential * r^2 * dr:
hartree(l, n2c, beta, N, vr)
nv = np.dot(n1c, vr)
# expansion coefficients
A_mm = X_ii[i1:i1 + 2 * lv1 + 1, i2:i2 + 2 * lv2 + 1]
for mc in range(2 * lc + 1):
for m in range(2 * l + 1):
G1c = gaunt[lv1**2:(lv1 + 1)**2,
lc**2 + mc, l**2 + m]
G2c = gaunt[lv2**2:(lv2 + 1)**2,
lc**2 + mc, l**2 + m]
A_mm += nv * np.outer(G1c, G2c)
i2 += 2 * lv2 + 1
i1 += 2 * lv1 + 1
# pack X_ii matrix
X_p = pack2(X_ii)
return X_p
def atomic_exact_exchange(atom, type = 'all'):
"""Returns the exact exchange energy of the atom defined by the
instantiated AllElectron object 'atom'
"""
gaunt = make_gaunt(lmax=max(atom.l_j)) # Make gaunt coeff. list
Nj = len(atom.n_j) # The total number of orbitals
# determine relevant states for chosen type of exchange contribution
if type == 'all':
nstates = mstates = range(Nj)
else:
Njcore = core_states(atom.symbol) # The number of core orbitals
if type == 'val-val':
nstates = mstates = range(Njcore, Nj)
elif type == 'core-core':
nstates = mstates = range(Njcore)
elif type == 'val-core':
nstates = range(Njcore,Nj)
mstates = range(Njcore)
else:
raise RuntimeError('Unknown type of exchange: ', type)
# Arrays for storing the potential (times radius)
vr = np.zeros(atom.N)
vrl = np.zeros(atom.N)
# do actual calculation of exchange contribution
Exx = 0.0
for j1 in nstates:
# angular momentum of first state
l1 = atom.l_j[j1]
for j2 in mstates:
# angular momentum of second state
l2 = atom.l_j[j2]
# joint occupation number
f12 = .5 * atom.f_j[j1] / (2. * l1 + 1) * \
atom.f_j[j2] / (2. * l2 + 1)
# electron density times radius times length element
nrdr = atom.u_j[j1] * atom.u_j[j2] * atom.dr
nrdr[1:] /= atom.r[1:]
# potential times radius
vr[:] = 0.0
# L summation
for l in range(l1 + l2 + 1):
# get potential for current l-value
hartree(l, nrdr, atom.beta, atom.N, vrl)
# take all m1 m2 and m values of Gaunt matrix of the form
# G(L1,L2,L) where L = {l,m}
G2 = gaunt[l1**2:(l1+1)**2, l2**2:(l2+1)**2, l**2:(l+1)**2]**2
# add to total potential
vr += vrl * np.sum(G2)
# add to total exchange the contribution from current two states
Exx += -.5 * f12 * np.dot(vr, nrdr)
# double energy if mixed contribution
if type == 'val-core': Exx *= 2.
# return exchange energy
return Exx
def constructX(gen):
"""Construct the X_p^a matrix for the given atom.
The X_p^a matrix describes the valence-core interactions of the
partial waves.
"""
# initialize attributes
uv_j = gen.vu_j # soft valence states * r:
lv_j = gen.vl_j # their repective l quantum numbers
Nvi = 0
for l in lv_j:
Nvi += 2 * l + 1 # total number of valence states (including m)
# number of core and valence orbitals (j only, i.e. not m-number)
Njcore = gen.njcore
Njval = len(lv_j)
# core states * r:
uc_j = gen.u_j[:Njcore]
r, dr, N, beta = gen.r, gen.dr, gen.N, gen.beta
# potential times radius
vr = np.zeros(N)
# initialize X_ii matrix
X_ii = np.zeros((Nvi, Nvi))
# make gaunt coeff. list
lmax = max(gen.l_j[:Njcore] + gen.vl_j)
gaunt = make_gaunt(lmax=lmax)
# sum over core states
for jc in range(Njcore):
lc = gen.l_j[jc]
# sum over first valence state index
i1 = 0
for jv1 in range(Njval):
lv1 = lv_j[jv1]
# electron density 1 times radius times length element
n1c = uv_j[jv1] * uc_j[jc] * dr
n1c[1:] /= r[1:]
# sum over second valence state index
i2 = 0
for jv2 in range(Njval):
lv2 = lv_j[jv2]
# electron density 2
n2c = uv_j[jv2] * uc_j[jc] * dr
n2c[1:] /= r[1:]
# sum expansion in angular momenta
for l in range(min(lv1, lv2) + lc + 1):
# Int density * potential * r^2 * dr:
hartree(l, n2c, r, vr)
nv = np.dot(n1c, vr)
# expansion coefficients
A_mm = X_ii[i1:i1 + 2 * lv1 + 1, i2:i2 + 2 * lv2 + 1]
for mc in range(2 * lc + 1):
for m in range(2 * l + 1):
G1c = gaunt[lv1**2:(lv1 + 1)**2, lc**2 + mc,
l**2 + m]
G2c = gaunt[lv2**2:(lv2 + 1)**2, lc**2 + mc,
l**2 + m]
A_mm += nv * np.outer(G1c, G2c)
i2 += 2 * lv2 + 1
i1 += 2 * lv1 + 1
# pack X_ii matrix
X_p = pack2(X_ii)
return X_p
def atomic_exact_exchange(atom, type='all'):
"""Returns the exact exchange energy of the atom defined by the
instantiated AllElectron object 'atom'
"""
gaunt = make_gaunt(lmax=max(atom.l_j)) # Make gaunt coeff. list
Nj = len(atom.n_j) # The total number of orbitals
# determine relevant states for chosen type of exchange contribution
if type == 'all':
nstates = mstates = range(Nj)
else:
Njcore = core_states(atom.symbol) # The number of core orbitals
if type == 'val-val':
nstates = mstates = range(Njcore, Nj)
elif type == 'core-core':
nstates = mstates = range(Njcore)
elif type == 'val-core':
nstates = range(Njcore, Nj)
mstates = range(Njcore)
else:
raise RuntimeError('Unknown type of exchange: ', type)
# Arrays for storing the potential (times radius)
vr = np.zeros(atom.N)
vrl = np.zeros(atom.N)
# do actual calculation of exchange contribution
Exx = 0.0
for j1 in nstates:
# angular momentum of first state
l1 = atom.l_j[j1]
for j2 in mstates:
# angular momentum of second state
l2 = atom.l_j[j2]
# joint occupation number
f12 = .5 * atom.f_j[j1] / (2. * l1 + 1) * \
atom.f_j[j2] / (2. * l2 + 1)
# electron density times radius times length element
nrdr = atom.u_j[j1] * atom.u_j[j2] * atom.dr
nrdr[1:] /= atom.r[1:]
# potential times radius
vr[:] = 0.0
# L summation
for l in range(l1 + l2 + 1):
# get potential for current l-value
hartree(l, nrdr, atom.r, vrl)
# take all m1 m2 and m values of Gaunt matrix of the form
# G(L1,L2,L) where L = {l,m}
G2 = gaunt[l1**2:(l1 + 1)**2, l2**2:(l2 + 1)**2,
l**2:(l + 1)**2]**2
# add to total potential
vr += vrl * np.sum(G2)
# add to total exchange the contribution from current two states
Exx += -.5 * f12 * np.dot(vr, nrdr)
# double energy if mixed contribution
if type == 'val-core': Exx *= 2.
# return exchange energy
return Exx
def calculate_exx_integrals(self):
# Find core states:
core = []
lmax = 0
for l, ch in enumerate(self.aea.channels):
for n, phi_g in enumerate(ch.phi_ng):
if (l >= len(self.waves_l)
or (l < len(self.waves_l)
and n + l + 1 not in self.waves_l[l].n_n)):
core.append((l, phi_g))
if l > lmax:
lmax = l
lmax = max(lmax, len(self.waves_l) - 1)
G_LLL = make_gaunt(lmax)
# Calculate core contribution to EXX energy:
self.exxcc = 0.0
j1 = 0
for l1, phi1_g in core:
f = 1.0
for l2, phi2_g in core[j1:]:
n_g = phi1_g * phi2_g
for l in range((l1 + l2) % 2, l1 + l2 + 1, 2):
G = (G_LLL[l1**2:(l1 + 1)**2, l2**2:(l2 + 1)**2,
l**2:(l + 1)**2]**2).sum()
vr_g = self.rgd.poisson(n_g, l)
e = f * self.rgd.integrate(vr_g * n_g, -1) / 4 / pi
self.exxcc -= e * G
f = 2.0
j1 += 1
self.log('EXX (core-core):', self.exxcc, 'Hartree')
# Calculate core-valence contribution to EXX energy:
ni = sum(
len(waves) * (2 * l + 1) for l, waves in enumerate(self.waves_l))
self.exxcv_ii = np.zeros((ni, ni))
i1 = 0
for l1, waves1 in enumerate(self.waves_l):
for phi1_g in waves1.phi_ng:
i2 = 0
for l2, waves2 in enumerate(self.waves_l):
for phi2_g in waves2.phi_ng:
X_mm = self.exxcv_ii[i1:i1 + 2 * l1 + 1,
i2:i2 + 2 * l2 + 1]
if (l1 + l2) % 2 == 0:
for lc, phi_g in core:
n_g = phi1_g * phi_g
for l in range((l1 + lc) % 2,
max(l1, l2) + lc + 1, 2):
vr_g = self.rgd.poisson(phi2_g * phi_g, l)
e = (self.rgd.integrate(vr_g * n_g, -1) /
(4 * pi))
for mc in range(2 * lc + 1):
for m in range(2 * l + 1):
G_L = G_LLL[:, lc**2 + mc,
l**2 + m]
X_mm += np.outer(
G_L[l1**2:(l1 + 1)**2],
G_L[l2**2:(l2 + 1)**2]) * e
i2 += 2 * l2 + 1
i1 += 2 * l1 + 1