"""Resonant Raman intensities"""
import sys
from pathlib import Path
import numpy as np
import ase.units as u
from ase.parallel import paropen, parprint, world
from ase.vibrations import Vibrations
from ase.vibrations.raman import Raman, RamanCalculatorBase
[docs]class ResonantRamanCalculator(RamanCalculatorBase, Vibrations):
"""Base class for resonant Raman calculators using finite differences.
"""
def __init__(self, atoms, ExcitationsCalculator, *args,
exkwargs=None, exext='.ex.gz', overlap=False,
**kwargs):
"""
Parameters
----------
atoms: Atoms
The Atoms object
ExcitationsCalculator: object
Calculator for excited states
exkwargs: dict
Arguments given to the ExcitationsCalculator object
exext: string
Extension for filenames of Excitation lists (results of
the ExcitationsCalculator).
overlap : function or False
Function to calculate overlaps between excitation at
equilibrium and at a displaced position. Calculators are
given as first and second argument, respectively.
Example
-------
>>> from ase.calculators.h2morse import (H2Morse,
... H2MorseExcitedStatesCalculator)
>>> from ase.vibrations.resonant_raman import ResonantRamanCalculator
>>>
>>> atoms = H2Morse()
>>> rmc = ResonantRamanCalculator(atoms, H2MorseExcitedStatesCalculator)
>>> rmc.run()
This produces all necessary data for further analysis.
"""
self.exobj = ExcitationsCalculator
if exkwargs is None:
exkwargs = {}
self.exkwargs = exkwargs
self.overlap = overlap
super().__init__(atoms, *args, exext=exext, **kwargs)
def _new_exobj(self):
# XXXX I have to duplicate this because there are two objects
# which have exkwargs, why are they not unified?
return self.exobj(**self.exkwargs)
def calculate(self, atoms, disp):
"""Call ground and excited state calculation"""
assert atoms == self.atoms # XXX action required
forces = self.atoms.get_forces()
if self.overlap:
"""Overlap is determined as
ov_ij = int dr displaced*_i(r) eqilibrium_j(r)
"""
ov_nn = self.overlap(self.atoms.calc,
self.eq_calculator)
if world.rank == 0:
disp.save_ov_nn(ov_nn)
disp.calculate_and_save_exlist(atoms)
return {'forces': forces}
def run(self):
if self.overlap:
# XXXX stupid way to make a copy
self.atoms.get_potential_energy()
self.eq_calculator = self.atoms.calc
Path(self.name).mkdir(parents=True, exist_ok=True)
fname = Path(self.name) / 'tmp.gpw'
self.eq_calculator.write(fname, 'all')
self.eq_calculator = self.eq_calculator.__class__(restart=fname)
try:
# XXX GPAW specific
self.eq_calculator.converge_wave_functions()
except AttributeError:
pass
Vibrations.run(self)
class ResonantRaman(Raman):
"""Base Class for resonant Raman intensities using finite differences.
"""
def __init__(self, atoms, Excitations, *args,
observation=None,
form='v', # form of the dipole operator
exkwargs=None, # kwargs to be passed to Excitations
exext='.ex.gz', # extension for Excitation names
overlap=False,
minoverlap=0.02,
minrep=0.8,
comm=world,
**kwargs):
"""
Parameters
----------
atoms: ase Atoms object
Excitations: class
Type of the excitation list object. The class object is
initialized as::
Excitations(atoms.calc)
or by reading form a file as::
Excitations('filename', **exkwargs)
The file is written by calling the method
Excitations.write('filename').
Excitations should work like a list of ex obejects, where:
ex.get_dipole_me(form='v'):
gives the velocity form dipole matrix element in
units |e| * Angstrom
ex.energy:
is the transition energy in Hartrees
approximation: string
Level of approximation used.
observation: dict
Polarization settings
form: string
Form of the dipole operator, 'v' for velocity form (default)
and 'r' for length form.
overlap: bool or function
Use wavefunction overlaps.
minoverlap: float ord dict
Minimal absolute overlap to consider. Defaults to 0.02 to avoid
numerical garbage.
minrep: float
Minimal representation to consider derivative, defaults to 0.8
"""
if observation is None:
observation = {'geometry': '-Z(XX)Z'}
kwargs['exext'] = exext
Raman.__init__(self, atoms, *args, **kwargs)
assert self.vibrations.nfree == 2
self.exobj = Excitations
if exkwargs is None:
exkwargs = {}
self.exkwargs = exkwargs
self.observation = observation
self.dipole_form = form
self.overlap = overlap
if not isinstance(minoverlap, dict):
# assume it's a number
self.minoverlap = {'orbitals': minoverlap,
'excitations': minoverlap}
else:
self.minoverlap = minoverlap
self.minrep = minrep
def read_exobj(self, filename):
return self.exobj.read(filename, **self.exkwargs)
def get_absolute_intensities(self, omega, gamma=0.1, delta=0, **kwargs):
"""Absolute Raman intensity or Raman scattering factor
Parameter
---------
omega: float
incoming laser energy, unit eV
gamma: float
width (imaginary energy), unit eV
delta: float
pre-factor for asymmetric anisotropy, default 0
References
----------
Porezag and Pederson, PRB 54 (1996) 7830-7836 (delta=0)
Baiardi and Barone, JCTC 11 (2015) 3267-3280 (delta=5)
Returns
-------
raman intensity, unit Ang**4/amu
"""
alpha2_r, gamma2_r, delta2_r = self._invariants(
self.electronic_me_Qcc(omega, gamma, **kwargs))
return 45 * alpha2_r + delta * delta2_r + 7 * gamma2_r
@property
def approximation(self):
return self._approx
@approximation.setter
def approximation(self, value):
self.set_approximation(value)
def read_excitations(self):
"""Read all finite difference excitations and select matching."""
if self.overlap:
return self.read_excitations_overlap()
disp = self._eq_disp()
ex0_object = disp.read_exobj()
eu = ex0_object.energy_to_eV_scale
matching = frozenset(ex0_object)
def append(lst, disp, matching):
exo = disp.read_exobj()
lst.append(exo)
matching = matching.intersection(exo)
return matching
exm_object_list = []
exp_object_list = []
for a, i in zip(self.myindices, self.myxyz):
mdisp = self._disp(a, i, -1)
pdisp = self._disp(a, i, 1)
matching = append(exm_object_list,
mdisp, matching)
matching = append(exp_object_list,
pdisp, matching)
def select(exl, matching):
mlst = [ex for ex in exl if ex in matching]
assert len(mlst) == len(matching)
return mlst
ex0 = select(ex0_object, matching)
exm = []
exp = []
r = 0
for a, i in zip(self.myindices, self.myxyz):
exm.append(select(exm_object_list[r], matching))
exp.append(select(exp_object_list[r], matching))
r += 1
self.ex0E_p = np.array([ex.energy * eu for ex in ex0])
self.ex0m_pc = (np.array(
[ex.get_dipole_me(form=self.dipole_form) for ex in ex0]) *
u.Bohr)
exmE_rp = []
expE_rp = []
exF_rp = []
exmm_rpc = []
expm_rpc = []
r = 0
for a, i in zip(self.myindices, self.myxyz):
exmE_rp.append([em.energy for em in exm[r]])
expE_rp.append([ep.energy for ep in exp[r]])
exF_rp.append(
[(em.energy - ep.energy)
for ep, em in zip(exp[r], exm[r])])
exmm_rpc.append(
[ex.get_dipole_me(form=self.dipole_form)
for ex in exm[r]])
expm_rpc.append(
[ex.get_dipole_me(form=self.dipole_form)
for ex in exp[r]])
r += 1
# indicees: r=coordinate, p=excitation
# energies in eV
self.exmE_rp = np.array(exmE_rp) * eu
self.expE_rp = np.array(expE_rp) * eu
# forces in eV / Angstrom
self.exF_rp = np.array(exF_rp) * eu / 2 / self.delta
# matrix elements in e * Angstrom
self.exmm_rpc = np.array(exmm_rpc) * u.Bohr
self.expm_rpc = np.array(expm_rpc) * u.Bohr
def read_excitations_overlap(self):
"""Read all finite difference excitations and wf overlaps.
We assume that the wave function overlaps are determined as
ov_ij = int dr displaced*_i(r) eqilibrium_j(r)
"""
ex0 = self._eq_disp().read_exobj()
eu = ex0.energy_to_eV_scale
rep0_p = np.ones((len(ex0)), dtype=float)
def load(disp, rep0_p):
ex_p = disp.read_exobj()
ov_nn = disp.load_ov_nn()
# remove numerical garbage
ov_nn = np.where(np.abs(ov_nn) > self.minoverlap['orbitals'],
ov_nn, 0)
ov_pp = ex_p.overlap(ov_nn, ex0)
ov_pp = np.where(np.abs(ov_pp) > self.minoverlap['excitations'],
ov_pp, 0)
rep0_p *= (ov_pp.real**2 + ov_pp.imag**2).sum(axis=0)
return ex_p, ov_pp
def rotate(ex_p, ov_pp):
e_p = np.array([ex.energy for ex in ex_p])
m_pc = np.array(
[ex.get_dipole_me(form=self.dipole_form) for ex in ex_p])
r_pp = ov_pp.T
return ((r_pp.real**2 + r_pp.imag**2).dot(e_p),
r_pp.dot(m_pc))
exmE_rp = []
expE_rp = []
exF_rp = []
exmm_rpc = []
expm_rpc = []
exdmdr_rpc = []
for a, i in zip(self.myindices, self.myxyz):
mdisp = self._disp(a, i, -1)
pdisp = self._disp(a, i, 1)
ex, ov = load(mdisp, rep0_p)
exmE_p, exmm_pc = rotate(ex, ov)
ex, ov = load(pdisp, rep0_p)
expE_p, expm_pc = rotate(ex, ov)
exmE_rp.append(exmE_p)
expE_rp.append(expE_p)
exF_rp.append(exmE_p - expE_p)
exmm_rpc.append(exmm_pc)
expm_rpc.append(expm_pc)
exdmdr_rpc.append(expm_pc - exmm_pc)
# select only excitations that are sufficiently represented
self.comm.product(rep0_p)
select = np.where(rep0_p > self.minrep)[0]
self.ex0E_p = np.array([ex.energy * eu for ex in ex0])[select]
self.ex0m_pc = (np.array(
[ex.get_dipole_me(form=self.dipole_form)
for ex in ex0])[select] * u.Bohr)
if len(self.myr):
# indicees: r=coordinate, p=excitation
# energies in eV
self.exmE_rp = np.array(exmE_rp)[:, select] * eu
self.expE_rp = np.array(expE_rp)[:, select] * eu
# forces in eV / Angstrom
self.exF_rp = np.array(exF_rp)[:, select] * eu / 2 / self.delta
# matrix elements in e * Angstrom
self.exmm_rpc = np.array(exmm_rpc)[:, select, :] * u.Bohr
self.expm_rpc = np.array(expm_rpc)[:, select, :] * u.Bohr
# matrix element derivatives in e
self.exdmdr_rpc = (np.array(exdmdr_rpc)[:, select, :] *
u.Bohr / 2 / self.delta)
else:
# did not read
self.exmE_rp = self.expE_rp = self.exF_rp = np.empty(0)
self.exmm_rpc = self.expm_rpc = self.exdmdr_rpc = np.empty(0)
def read(self, *args, **kwargs):
"""Read data from a pre-performed calculation."""
self.vibrations.read(*args, **kwargs)
self.init_parallel_read()
if not hasattr(self, 'ex0E_p'):
if self.overlap:
self.read_excitations_overlap()
else:
self.read_excitations()
self._already_read = True
def get_cross_sections(self, omega, gamma):
"""Returns Raman cross sections for each vibration."""
I_v = self.intensity(omega, gamma)
pre = 1. / 16 / np.pi**2 / u._eps0**2 / u._c**4
# frequency of scattered light
omS_v = omega - self.om_Q
return pre * omega * omS_v**3 * I_v
def get_spectrum(self, omega, gamma=0.1,
start=None, end=None, npts=None, width=20,
type='Gaussian',
intensity_unit='????', normalize=False):
"""Get resonant Raman spectrum.
The method returns wavenumbers in cm^-1 with corresponding
Raman cross section.
Start and end point, and width of the Gaussian/Lorentzian should
be given in cm^-1.
"""
self.type = type.lower()
assert self.type in ['gaussian', 'lorentzian']
frequencies = self.get_energies().real / u.invcm
intensities = self.get_cross_sections(omega, gamma)
if width is None:
return [frequencies, intensities]
if start is None:
start = min(self.om_Q) / u.invcm - 3 * width
if end is None:
end = max(self.om_Q) / u.invcm + 3 * width
if not npts:
npts = int((end - start) / width * 10 + 1)
prefactor = 1
if self.type == 'lorentzian':
intensities = intensities * width * np.pi / 2.
if normalize:
prefactor = 2. / width / np.pi
else:
sigma = width / 2. / np.sqrt(2. * np.log(2.))
if normalize:
prefactor = 1. / sigma / np.sqrt(2 * np.pi)
# Make array with spectrum data
spectrum = np.empty(npts)
energies = np.linspace(start, end, npts)
for i, energy in enumerate(energies):
energies[i] = energy
if self.type == 'lorentzian':
spectrum[i] = (intensities * 0.5 * width / np.pi /
((frequencies - energy)**2 +
0.25 * width**2)).sum()
else:
spectrum[i] = (intensities *
np.exp(-(frequencies - energy)**2 /
2. / sigma**2)).sum()
return [energies, prefactor * spectrum]
def write_spectrum(self, omega, gamma,
out='resonant-raman-spectra.dat',
start=200, end=4000,
npts=None, width=10,
type='Gaussian'):
"""Write out spectrum to file.
Start and end
point, and width of the Gaussian/Lorentzian should be given
in cm^-1."""
energies, spectrum = self.get_spectrum(omega, gamma,
start, end, npts, width,
type)
# Write out spectrum in file. First column is absolute intensities.
outdata = np.empty([len(energies), 3])
outdata.T[0] = energies
outdata.T[1] = spectrum
with paropen(out, 'w') as fd:
fd.write('# Resonant Raman spectrum\n')
if hasattr(self, '_approx'):
fd.write(f'# approximation: {self._approx}\n')
for key in self.observation:
fd.write(f'# {key}: {self.observation[key]}\n')
fd.write('# omega={:g} eV, gamma={:g} eV\n'
.format(omega, gamma))
if width is not None:
fd.write('# %s folded, width=%g cm^-1\n'
% (type.title(), width))
fd.write('# [cm^-1] [a.u.]\n')
for row in outdata:
fd.write('%.3f %15.5g\n' %
(row[0], row[1]))
def summary(self, omega, gamma=0.1,
method='standard', direction='central',
log=sys.stdout):
"""Print summary for given omega [eV]"""
self.read(method, direction)
hnu = self.get_energies()
intensities = self.get_absolute_intensities(omega, gamma)
te = int(np.log10(intensities.max())) - 2
scale = 10**(-te)
if not te:
ts = ''
elif te > -2 and te < 3:
ts = str(10**te)
else:
ts = f'10^{te}'
if isinstance(log, str):
log = paropen(log, 'a')
parprint('-------------------------------------', file=log)
parprint(' excitation at ' + str(omega) + ' eV', file=log)
parprint(' gamma ' + str(gamma) + ' eV', file=log)
parprint(' method:', self.vibrations.method, file=log)
parprint(' approximation:', self.approximation, file=log)
parprint(' Mode Frequency Intensity', file=log)
parprint(f' # meV cm^-1 [{ts}A^4/amu]', file=log)
parprint('-------------------------------------', file=log)
for n, e in enumerate(hnu):
if e.imag != 0:
c = 'i'
e = e.imag
else:
c = ' '
e = e.real
parprint('%3d %6.1f%s %7.1f%s %9.2f' %
(n, 1000 * e, c, e / u.invcm, c, intensities[n] * scale),
file=log)
parprint('-------------------------------------', file=log)
parprint('Zero-point energy: %.3f eV' %
self.vibrations.get_zero_point_energy(),
file=log)
class LrResonantRaman(ResonantRaman):
"""Resonant Raman for linear response
Quick and dirty approach to enable loading of LrTDDFT calculations
"""
def read_excitations(self):
eq_disp = self._eq_disp()
ex0_object = eq_disp.read_exobj()
eu = ex0_object.energy_to_eV_scale
matching = frozenset(ex0_object.kss)
def append(lst, disp, matching):
exo = disp.read_exobj()
lst.append(exo)
matching = matching.intersection(exo.kss)
return matching
exm_object_list = []
exp_object_list = []
for a in self.indices:
for i in 'xyz':
disp1 = self._disp(a, i, -1)
disp2 = self._disp(a, i, 1)
matching = append(exm_object_list,
disp1,
matching)
matching = append(exp_object_list,
disp2,
matching)
def select(exl, matching):
exl.diagonalize(**self.exkwargs)
mlist = list(exl)
# mlst = [ex for ex in exl if ex in matching]
# assert(len(mlst) == len(matching))
return mlist
ex0 = select(ex0_object, matching)
exm = []
exp = []
r = 0
for a in self.indices:
for i in 'xyz':
exm.append(select(exm_object_list[r], matching))
exp.append(select(exp_object_list[r], matching))
r += 1
self.ex0E_p = np.array([ex.energy * eu for ex in ex0])
# self.exmE_p = np.array([ex.energy * eu for ex in exm])
# self.expE_p = np.array([ex.energy * eu for ex in exp])
self.ex0m_pc = (np.array(
[ex.get_dipole_me(form=self.dipole_form) for ex in ex0]) *
u.Bohr)
self.exF_rp = []
exmE_rp = []
expE_rp = []
exmm_rpc = []
expm_rpc = []
r = 0
for a in self.indices:
for i in 'xyz':
exmE_rp.append([em.energy for em in exm[r]])
expE_rp.append([ep.energy for ep in exp[r]])
self.exF_rp.append(
[(em.energy - ep.energy)
for ep, em in zip(exp[r], exm[r])])
exmm_rpc.append(
[ex.get_dipole_me(form=self.dipole_form) for ex in exm[r]])
expm_rpc.append(
[ex.get_dipole_me(form=self.dipole_form) for ex in exp[r]])
r += 1
self.exmE_rp = np.array(exmE_rp) * eu
self.expE_rp = np.array(expE_rp) * eu
self.exF_rp = np.array(self.exF_rp) * eu / 2 / self.delta
self.exmm_rpc = np.array(exmm_rpc) * u.Bohr
self.expm_rpc = np.array(expm_rpc) * u.Bohr