def test_franck_condon(testdir):
# FCOverlap
fco = FranckCondonOverlap()
fcr = FranckCondonRecursive()
# check factorial
assert (fco.factorial(8) == factorial(8))
# the second test is useful according to the implementation
assert (fco.factorial(5) == factorial(5))
assert (fco.factorial.inv(5) == 1. / factorial(5))
# check T=0 and n=0 equality
S = np.array([1, 2.1, 34])
m = 5
assert (((fco.directT0(m, S) - fco.direct(0, m, S)) / fco.directT0(m, S) <
1e-15).all())
# check symmetry
S = 2
n = 3
assert (fco.direct(n, m, S) == fco.direct(m, n, S))
# ---------------------------
# specials
S = np.array([0, 1.5])
delta = np.sqrt(2 * S)
for m in [2, 7]:
equal(
fco.direct0mm1(m, S)**2,
fco.direct(1, m, S) * fco.direct(m, 0, S), 1.e-17)
equal(fco.direct0mm1(m, S), fcr.ov0mm1(m, delta), 1.e-15)
equal(fcr.ov0mm1(m, delta),
fcr.ov0m(m, delta) * fcr.ov1m(m, delta), 1.e-15)
equal(fcr.ov0mm1(m, -delta), fcr.direct0mm1(m, -delta), 1.e-15)
equal(fcr.ov0mm1(m, delta), -fcr.direct0mm1(m, -delta), 1.e-15)
equal(
fco.direct0mm2(m, S)**2,
fco.direct(2, m, S) * fco.direct(m, 0, S), 1.e-17)
equal(fco.direct0mm2(m, S), fcr.ov0mm2(m, delta), 1.e-15)
equal(fcr.ov0mm2(m, delta),
fcr.ov0m(m, delta) * fcr.ov2m(m, delta), 1.e-15)
equal(fco.direct0mm2(m, S), fcr.direct0mm2(m, delta), 1.e-15)
equal(fcr.direct0mm3(m, delta),
fcr.ov0m(m, delta) * fcr.ov3m(m, delta), 1.e-15)
equal(fcr.ov1mm2(m, delta),
fcr.ov1m(m, delta) * fcr.ov2m(m, delta), 1.e-15)
equal(fcr.direct1mm2(m, delta), fcr.ov1mm2(m, delta), 1.e-15)
def get_matrix_element_AlbrechtA(self, omega, gamma=0.1, ml=range(16)):
"""Evaluate Albrecht A term.
Unit: |e|^2Angstrom^2/eV
"""
self.read()
self.timer.start('AlbrechtA')
if not hasattr(self, 'fco'):
self.fco = FranckCondonOverlap()
# excited state forces
F_pr = self.exF_rp.T
m_rcc = np.zeros((self.ndof, 3, 3), dtype=complex)
for p, energy in enumerate(self.ex0E_p):
S_r = self.get_Huang_Rhys_factors(F_pr[p])
me_cc = np.outer(self.ex0m_pc[p], self.ex0m_pc[p].conj())
for m in ml:
self.timer.start('0mm1')
fco_r = self.fco.direct0mm1(m, S_r)
self.timer.stop('0mm1')
self.timer.start('einsum')
m_rcc += np.einsum(
'a,bc->abc',
fco_r / (energy + m * self.om_r - omega - 1j * gamma),
me_cc)
m_rcc += np.einsum(
'a,bc->abc', fco_r /
(energy + (m - 1) * self.om_r + omega + 1j * gamma), me_cc)
self.timer.stop('einsum')
self.timer.stop('AlbrechtA')
return m_rcc
def test_franck_condon():
import sys
import numpy as np
from ase.vibrations.franck_condon import FranckCondonOverlap, FranckCondonRecursive
from math import factorial
def equal(x, y, tolerance=0, fail=True, msg=''):
"""Compare x and y."""
if not np.isfinite(x - y).any() or (np.abs(x - y) > tolerance).any():
msg = (msg + '%s != %s (error: |%s| > %.9g)' %
(x, y, x - y, tolerance))
if fail:
raise AssertionError(msg)
else:
sys.stderr.write('WARNING: %s\n' % msg)
# FCOverlap
fco = FranckCondonOverlap()
fcr = FranckCondonRecursive()
# check factorial
assert(fco.factorial(8) == factorial(8))
# the second test is useful according to the implementation
assert(fco.factorial(5) == factorial(5))
assert(fco.factorial.inv(5) == 1. / factorial(5))
# check T=0 and n=0 equality
S = np.array([1, 2.1, 34])
m = 5
assert(((fco.directT0(m, S) - fco.direct(0, m, S)) / fco.directT0(m, S) <
1e-15).all())
# check symmetry
S = 2
n = 3
assert(fco.direct(n, m, S) == fco.direct(m, n, S))
# ---------------------------
# specials
S = np.array([0, 1.5])
delta = np.sqrt(2 * S)
for m in [2, 7]:
equal(fco.direct0mm1(m, S)**2,
fco.direct(1, m, S) * fco.direct(m, 0, S), 1.e-17)
equal(fco.direct0mm1(m, S), fcr.ov0mm1(m, delta), 1.e-15)
equal(fcr.ov0mm1(m, delta),
fcr.ov0m(m, delta) * fcr.ov1m(m, delta), 1.e-15)
equal(fcr.ov0mm1(m, -delta), fcr.direct0mm1(m, -delta), 1.e-15)
equal(fcr.ov0mm1(m, delta), - fcr.direct0mm1(m, -delta), 1.e-15)
equal(fco.direct0mm2(m, S)**2,
fco.direct(2, m, S) * fco.direct(m, 0, S), 1.e-17)
equal(fco.direct0mm2(m, S), fcr.ov0mm2(m, delta), 1.e-15)
equal(fcr.ov0mm2(m, delta),
fcr.ov0m(m, delta) * fcr.ov2m(m, delta), 1.e-15)
equal(fco.direct0mm2(m, S), fcr.direct0mm2(m, delta), 1.e-15)
equal(fcr.direct0mm3(m, delta),
fcr.ov0m(m, delta) * fcr.ov3m(m, delta), 1.e-15)
equal(fcr.ov1mm2(m, delta),
fcr.ov1m(m, delta) * fcr.ov2m(m, delta), 1.e-15)
equal(fcr.direct1mm2(m, delta), fcr.ov1mm2(m, delta), 1.e-15)
def meBC(self, omega, gamma=0.1, term='BC'):
"""Evaluate Albrecht BC term.
Returns
-------
Full Albrecht BC matrix element.
Unit: e^2 Angstrom / eV / sqrt(amu)
"""
self.read()
if not hasattr(self, 'fco'):
self.fco = FranckCondonOverlap()
omL = omega + 1j * gamma
omS_Q = omL - self.om_Q
# excited state forces
n_p, myp, exF_pr = self.init_parallel_excitations()
# derivatives after normal coordinates
exdmdr_rpc = self._collect_r(self.exdmdr_rpc, [n_p, 3],
self.ex0m_pc.dtype)
dmdq_qpc = (exdmdr_rpc.T * self.im_r).T # unit e / sqrt(amu)
dmdQ_Qpc = np.dot(dmdq_qpc.T, self.modes_Qq.T).T # unit e / sqrt(amu)
me_Qcc = np.zeros((self.ndof, 3, 3), dtype=complex)
for p in myp:
energy = self.ex0E_p[p]
S_Q = self.Huang_Rhys_factors(exF_pr[p])
# relaxed excited state energy
# # n_vQ = np.where(self.n_vQ > 0, 1, 0)
# # energy_v = energy - n_vQ.dot(self.om_Q * S_Q)
energy_Q = energy - self.om_Q * S_Q
# # me_cc = np.outer(self.ex0m_pc[p], self.ex0m_pc[p].conj())
m_c = self.ex0m_pc[p] # e Angstrom
dmdQ_Qc = dmdQ_Qpc[:, p] # e / sqrt(amu)
wBLS_Q = np.zeros((self.ndof), dtype=complex)
wBSL_Q = np.zeros((self.ndof), dtype=complex)
wCLS_Q = np.zeros((self.ndof), dtype=complex)
wCSL_Q = np.zeros((self.ndof), dtype=complex)
for m in range(self.nm):
f0mmQ1_Q = (self.fco.directT0(m, S_Q) +
np.sqrt(2) * self.fco.direct0mm2(m, S_Q))
f0Qmm1_Q = self.fco.direct(1, m, S_Q)
em_Q = energy_Q + m * self.om_Q
wBLS_Q += f0mmQ1_Q / (em_Q - omL)
wBSL_Q += f0Qmm1_Q / (em_Q - omL)
wCLS_Q += f0mmQ1_Q / (em_Q + omS_Q)
wCSL_Q += f0Qmm1_Q / (em_Q + omS_Q)
# unit e^2 Angstrom / sqrt(amu)
mdmdQ_Qcc = np.einsum('a,bc->bac', m_c, dmdQ_Qc.conj())
dmdQm_Qcc = np.einsum('ab,c->abc', dmdQ_Qc, m_c.conj())
if 'B' in term:
me_Qcc += np.multiply(wBLS_Q, mdmdQ_Qcc.T).T
me_Qcc += np.multiply(wBSL_Q, dmdQm_Qcc.T).T
if 'C' in term:
me_Qcc += np.multiply(wCLS_Q, mdmdQ_Qcc.T).T
me_Qcc += np.multiply(wCSL_Q, dmdQm_Qcc.T).T
self.comm.sum(me_Qcc)
return me_Qcc # unit e^2 Angstrom / eV / sqrt(amu)
def equal(x, y, tolerance=0, fail=True, msg=''):
"""Compare x and y."""
if not np.isfinite(x - y).any() or (np.abs(x - y) > tolerance).any():
msg = (msg + '%s != %s (error: |%s| > %.9g)' %
(x, y, x - y, tolerance))
if fail:
raise AssertionError(msg)
else:
sys.stderr.write('WARNING: %s\n' % msg)
# FCOverlap
fco = FranckCondonOverlap()
fcr = FranckCondonRecursive()
# check factorial
assert (fco.factorial(8) == factorial(8))
# the second test is useful according to the implementation
assert (fco.factorial(5) == factorial(5))
assert (fco.factorial.inv(5) == 1. / factorial(5))
# check T=0 and n=0 equality
S = np.array([1, 2.1, 34])
m = 5
assert (((fco.directT0(m, S) - fco.direct(0, m, S)) / fco.directT0(m, S) <
1e-15).all())
# check symmetry
def get_matrix_element_AlbrechtBC(self,
omega,
gamma=0.1,
ml=[1],
term='BC'):
"""Evaluate Albrecht B and/or C term(s)."""
self.read()
self.timer.start('AlbrechtBC')
if not hasattr(self, 'fco'):
self.fco = FranckCondonOverlap()
# excited state forces
F_pr = self.exF_rp.T
m_rcc = np.zeros((self.ndof, 3, 3), dtype=complex)
for p, energy in enumerate(self.ex0E_p):
S_r = self.get_Huang_Rhys_factors(F_pr[p])
for m in ml:
self.timer.start('Franck-Condon overlaps')
fc1mm1_r = self.fco.direct(1, m, S_r)
fc0mm02_r = self.fco.direct(0, m, S_r)
fc0mm02_r += np.sqrt(2) * self.fco.direct0mm2(m, S_r)
# XXXXX
fc1mm1_r[-1] = 1
fc0mm02_r[-1] = 1
print(m, fc1mm1_r[-1], fc0mm02_r[-1])
self.timer.stop('Franck-Condon overlaps')
self.timer.start('me dervivatives')
dm_rc = []
r = 0
for a in self.indices:
for i in 'xyz':
dm_rc.append(
(self.expm_rpc[r, p] - self.exmm_rpc[r, p]) *
self.im[r])
print('pm=', self.expm_rpc[r, p], self.exmm_rpc[r, p])
r += 1
dm_rc = np.array(dm_rc) / (2 * self.delta)
self.timer.stop('me dervivatives')
self.timer.start('map to modes')
# print('dm_rc[2], dm_rc[5]', dm_rc[2], dm_rc[5])
print('dm_rc=', dm_rc)
dm_rc = np.dot(dm_rc.T, self.modes.T).T
print('dm_rc[-1][2]', dm_rc[-1][2])
self.timer.stop('map to modes')
self.timer.start('multiply')
# me_cc = np.outer(self.ex0m_pc[p], self.ex0m_pc[p].conj())
for r in range(self.ndof):
if 'B' in term:
# XXXX
denom = (1. / (energy + m * 0 * self.om_r[r] - omega -
1j * gamma))
# ok print('denom=', denom)
m_rcc[r] += (
np.outer(dm_rc[r], self.ex0m_pc[p].conj()) *
fc1mm1_r[r] * denom)
if r == 5:
print('m_rcc[r]=', m_rcc[r][2, 2])
m_rcc[r] += (
np.outer(self.ex0m_pc[p], dm_rc[r].conj()) *
fc0mm02_r[r] * denom)
if 'C' in term:
denom = (1. /
(energy +
(m - 1) * self.om_r[r] + omega + 1j * gamma))
m_rcc[r] += (
np.outer(self.ex0m_pc[p], dm_rc[r].conj()) *
fc1mm1_r[r] * denom)
m_rcc[r] += (
np.outer(dm_rc[r], self.ex0m_pc[p].conj()) *
fc0mm02_r[r] * denom)
self.timer.stop('multiply')
print('m_rcc[-1]=', m_rcc[-1][2, 2])
self.timer.start('pre_r')
with np.errstate(divide='ignore'):
pre_r = np.where(self.om_r > 0,
np.sqrt(units._hbar**2 / 2. / self.om_r), 0)
# print('BC: pre_r=', pre_r)
for r, p in enumerate(pre_r):
m_rcc[r] *= p
self.timer.stop('pre_r')
self.timer.stop('AlbrechtBC')
return m_rcc