def setUp(self,verbose=False):
self.verbose = verbose
#
# PURE ELECTRONIC AGGREGATE
#
m1 = Molecule([0.0, 1.0])
m2 = Molecule([0.0, 1.0])
agg = Aggregate(molecules=[m1, m2])
agg.set_resonance_coupling(0,1, 0.1)
agg.build()
self.ham = agg.get_Hamiltonian()
KK12 = ProjectionOperator(1, 2, dim=self.ham.dim)
KK21 = ProjectionOperator(2, 1, dim=self.ham.dim)
self.rates = (1.0/100.0, 1.0/200.0)
self.sbi = SystemBathInteraction([KK12,KK21],
rates=self.rates)
self.sbi.set_system(agg)
#
# VIBRONIC AGGREGATE
#
vm1 = Molecule([0.0, 1.0])
vm2 = Molecule([0.0, 1.0])
mod1 = Mode(0.01)
mod2 = Mode(0.01)
vm1.add_Mode(mod1)
vm2.add_Mode(mod2)
mod1.set_nmax(0, 3)
mod1.set_nmax(1, 3)
mod2.set_nmax(0, 3)
mod2.set_nmax(1, 3)
vagg = Aggregate(molecules=[vm1, vm2])
vagg.set_resonance_coupling(0, 1, 0.1)
vagg.build()
self.vham = vagg.get_Hamiltonian()
self.vsbi = SystemBathInteraction([KK12, KK21], rates=self.rates)
self.vsbi.set_system(vagg)
def setUp(self, verbose=False):
self.verbose = verbose
#
# PURE ELECTRONIC AGGREGATE
#
m1 = Molecule([0.0, 1.0])
m2 = Molecule([0.0, 1.0])
agg = Aggregate(molecules=[m1, m2])
agg.set_resonance_coupling(0, 1, 0.1)
agg.build()
self.ham = agg.get_Hamiltonian()
KK12 = ProjectionOperator(1, 2, dim=self.ham.dim)
KK21 = ProjectionOperator(2, 1, dim=self.ham.dim)
self.rates = (1.0 / 100.0, 1.0 / 200.0)
self.sbi = SystemBathInteraction([KK12, KK21], rates=self.rates)
self.sbi.set_system(agg)
#
# VIBRONIC AGGREGATE
#
vm1 = Molecule([0.0, 1.0])
vm2 = Molecule([0.0, 1.0])
mod1 = Mode(0.01)
mod2 = Mode(0.01)
vm1.add_Mode(mod1)
vm2.add_Mode(mod2)
mod1.set_nmax(0, 3)
mod1.set_nmax(1, 3)
mod2.set_nmax(0, 3)
mod2.set_nmax(1, 3)
vagg = Aggregate(molecules=[vm1, vm2])
vagg.set_resonance_coupling(0, 1, 0.1)
vagg.build()
self.vham = vagg.get_Hamiltonian()
self.vsbi = SystemBathInteraction([KK12, KK21], rates=self.rates)
self.vsbi.set_system(vagg)
def test_abs_calculator(self):
"""Testing some basic methods of the AbsSpectrumCalculator class
"""
#Calculations for monomer are already performed. Now testing that
#absorption spectrum can be calculated for an aggregate.
try:
mol1 = Molecule(elenergies=[0.0, 12000.0])
mol2 = Molecule(elenergies=[0.0, 12000.0])
params = dict(ftype="OverdampedBrownian", reorg=20, cortime=100,
T=300)
mol1.set_dipole(0,1,[0.0, 1.0, 0.0])
mol2.set_dipole(0,1,[0.0, 1.0, 0.0])
cf = CorrelationFunction(self.ta, params)
mol1.set_transition_environment((0,1),cf)
mol2.set_transition_environment((0,1),cf)
agg = Aggregate(name="tester_dim", molecules=[mol1, mol2])
agg.build()
HH = agg.get_Hamiltonian()
abs_calc = AbsSpectrumCalculator(self.ta,
system=agg,
dynamics="secular",
relaxation_tensor=None,
rate_matrix=None)
abs_calc.bootstrap(rwa=12000)
abs_calc = abs_calc.calculate()
except:
raise Exception('Absorption not calculatable for aggregate')
def test_abs_calculator(self):
"""Testing some basic methods of the AbsSpectrumCalculator class
"""
#Calculations for monomer are already performed. Now testing that
#absorption spectrum can be calculated for an aggregate.
try:
mol1 = Molecule(elenergies=[0.0, 12000.0])
mol2 = Molecule(elenergies=[0.0, 12000.0])
params = dict(ftype="OverdampedBrownian", reorg=20, cortime=100,
T=300)
mol1.set_dipole(0,1,[0.0, 1.0, 0.0])
mol2.set_dipole(0,1,[0.0, 1.0, 0.0])
cf = CorrelationFunction(self.ta, params)
mol1.set_transition_environment((0,1),cf)
mol2.set_transition_environment((0,1),cf)
agg = Aggregate(name="tester_dim", molecules=[mol1, mol2])
agg.build()
HH = agg.get_Hamiltonian()
abs_calc = AbsSpectrumCalculator(self.ta,
system=agg,
dynamics="secular",
relaxation_tensor=None,
rate_matrix=None)
abs_calc.bootstrap(rwa=12000)
abs_calc = abs_calc.calculate()
except:
raise Exception('Absorption not calculatable for aggregate')
def hamiltonian_is_created(self):
#
# Homodimer
#
with energy_units(world.h_units):
en = world.senergy
m1 = Molecule([0.0, en], "mol1")
m2 = Molecule([0.0, en], "mol2")
agg = Aggregate(name="Homodimer")
agg.add_Molecule(m1)
agg.add_Molecule(m2)
with energy_units(world.r_units):
agg.set_resonance_coupling(0, 1, world.r_coupl)
agg.build()
world.HH = agg.get_Hamiltonian()
def hamiltonian_is_created(self):
#
# Homodimer
#
with energy_units(world.h_units):
en = world.senergy
m1 = Molecule([0.0, en], "mol1")
m2 = Molecule([0.0, en], "mol2")
agg = Aggregate(name="Homodimer")
agg.add_Molecule(m1)
agg.add_Molecule(m2)
with energy_units(world.r_units):
agg.set_resonance_coupling(0,1,world.r_coupl)
agg.build()
world.HH = agg.get_Hamiltonian()
class AggregateTest(unittest.TestCase):
"""Tests for the Manager class
"""
def setUp(self):
m1 = Molecule(name="Molecule 1", elenergies=[0.0, 1.0])
m2 = Molecule(name="Molecule 2", elenergies=[0.0, 1.0])
time = TimeAxis(0.0, 1000, 1.0)
params = dict(ftype="OverdampedBrownian", reorg=20, cortime=100, T=300)
with energy_units("1/cm"):
fc = CorrelationFunction(time, params)
m1.set_transition_environment((0, 1), fc)
m1.position = [0.0, 0.0, 0.0]
m1.set_dipole(0, 1, [10.0, 0.0, 0.0])
m2.set_transition_environment((0, 1), fc)
m2.position = [10.0, 0.0, 0.0]
m2.set_dipole(0, 1, [10.0, 0.0, 0.0])
self.agg = Aggregate(name="TestAgg", molecules=[m1, m2])
self.agg.set_coupling_by_dipole_dipole()
self.agg.build()
m3 = Molecule(name="Molecule 1", elenergies=[0.0, 1.0])
m4 = Molecule(name="Molecule 2", elenergies=[0.0, 1.0])
m3.add_Mode(Mode(0.01))
m4.add_Mode(Mode(0.01))
mod3 = m3.get_Mode(0)
mod4 = m4.get_Mode(0)
mod3.set_nmax(0, 4)
mod3.set_nmax(1, 4)
mod3.set_HR(1, 0.1)
mod4.set_nmax(0, 4)
mod4.set_nmax(1, 4)
mod4.set_HR(1, 0.3)
self.vagg = Aggregate(molecules=[m3, m4])
self.vagg.build()
#########################################################################
#
# TESTS
#
#########################################################################
def test_saving_of_aggregate(self):
"""(Aggregate) Testing its saving capability
"""
use_temporary_file = True
if use_temporary_file:
#drv = "core"
#bcs = False
#with h5py.File('tempfile.hdf5',
# driver=drv,
# backing_store=bcs) as f:
with tempfile.TemporaryFile() as f:
self.agg.save(f, test=True) #,report_unsaved=True)
# reread it
agg = Aggregate()
agg = agg.load(f, test=True)
else:
#with h5py.File('tempfile.hdf5') as f:
with open('tempfile.qrp', 'wb') as f:
self.agg.save(f)
#with h5py.File('tempfile.hdf5') as f:
with open('tempfile.qrp', 'rb') as f:
agg = Aggregate()
agg.load(f)
self.assertEqual(self.agg.nmono, agg.nmono)
self.assertEqual(self.agg.mult, agg.mult)
self.assertEqual(self.agg.sbi_mult, agg.sbi_mult)
self.assertEqual(self.agg.name, agg.name)
self.assertEqual(self.agg._has_egcf_matrix, agg._has_egcf_matrix)
self.assertEqual(self.agg._has_system_bath_interaction,
agg._has_system_bath_interaction)
self.assertEqual(self.agg.coupling_initiated, agg.coupling_initiated)
self.assertEqual(self.agg._has_relaxation_tensor,
agg._has_relaxation_tensor)
self.assertEqual(self.agg._relaxation_theory, agg._relaxation_theory)
self.assertEqual(self.agg._built, agg._built)
self.assertEqual(self.agg.Nel, agg.Nel)
self.assertEqual(self.agg.Ntot, agg.Ntot)
numpy.testing.assert_array_equal(self.agg.Nb, agg.Nb)
for key in agg.mnames.keys():
self.assertEqual(self.agg.mnames[key], agg.mnames[key])
numpy.testing.assert_array_equal(self.agg.resonance_coupling,
agg.resonance_coupling)
mnames = ["Molecule 1", "Molecule 2"]
for k in range(agg.nmono):
m = agg.monomers[k]
self.assertIn(m.name, mnames)
mnames.remove(m.name)
def test_trace_over_vibrations(self):
"""(Aggregate) Testing trace over vibrational DOF
"""
agg = self.vagg
ham = agg.get_Hamiltonian()
rho = ReducedDensityMatrix(dim=ham.dim)
rho._data[5, 5] = 1.0
redr = agg.trace_over_vibrations(rho)
numpy.testing.assert_almost_equal(numpy.trace(redr._data),
1.0,
decimal=7)
N = agg.Nb[0]
rho = ReducedDensityMatrix(dim=ham.dim)
rho._data[N + 5, N + 5] = 1.0
redr = agg.trace_over_vibrations(rho)
numpy.testing.assert_almost_equal(numpy.trace(redr._data),
1.0,
decimal=3)
N = agg.Nb[1]
rho = ReducedDensityMatrix(dim=ham.dim)
rho._data[N + 5, N + 5] = 1.0
redr = agg.trace_over_vibrations(rho)
numpy.testing.assert_almost_equal(numpy.trace(redr._data),
1.0,
decimal=2)
def test_get_Density_Matrix_thermal(self):
"""(Aggregate) Testing the get_Densitymatrix method with `thermal` condition type
"""
from quantarhei.core.units import kB_intK
vagg = self.vagg
H = vagg.get_Hamiltonian()
N = H.data.shape[0]
# zero temperature
rho0 = vagg.get_DensityMatrix(condition_type="thermal")
tst0 = numpy.zeros((N, N), dtype=qr.COMPLEX)
tst0[0, 0] = 1.0
numpy.testing.assert_almost_equal(rho0.data, tst0)
# room temperature
rho0 = vagg.get_DensityMatrix(condition_type="thermal",
temperature=300)
# cannonical balance between neighboring states is tested
kbT = kB_intK * 300.0
for k in range(N - 1):
E2 = H.data[k + 1, k + 1]
E1 = H.data[k, k]
ratio = numpy.exp(-(E2 - E1) / kbT)
numpy.testing.assert_almost_equal(
ratio, rho0.data[k + 1, k + 1] / rho0.data[k, k])
def test_get_Density_Matrix_thermal_excited(self):
"""(Aggregate) Testing the get_Densitymatrix method with `thermal_excited_state` condition type
"""
from quantarhei.core.units import kB_intK
vagg = self.vagg
H = vagg.get_Hamiltonian()
N = H.data.shape[0]
Nb0 = vagg.Nb[0]
# zero temperature
rho0 = vagg.get_DensityMatrix(condition_type="thermal_excited_state")
tst0 = numpy.zeros((N, N), dtype=qr.COMPLEX)
tst0[Nb0, Nb0] = 1.0
numpy.testing.assert_almost_equal(rho0.data, tst0)
# room temperature
kbT = kB_intK * 300.0
H = self.agg.get_Hamiltonian()
N = H.data.shape[0]
Nb0 = self.agg.Nb[0]
with qr.eigenbasis_of(H):
rho0 = self.agg.get_DensityMatrix(
condition_type="thermal_excited_state", temperature=300)
tst0 = numpy.zeros((N, N), dtype=qr.COMPLEX)
with qr.eigenbasis_of(H):
ssum = 0.0
for i in range(Nb0, N):
tst0[i,
i] = numpy.exp(-(H.data[i, i] - H.data[Nb0, Nb0]) / kbT)
ssum += tst0[i, i]
tst0 = tst0 / ssum
numpy.testing.assert_almost_equal(rho0.data, tst0)
# ssum = 0.0
# for i in range(N):
# tst0[i,i] = numpy.exp(-H.data[i,i]/kbT)
# ssum += tst0[i,i]
# tst0 = tst0/ssum
#
# DD = vagg.TrDMOp.data
# # abs value of the transition dipole moment
# dabs = numpy.sqrt(DD[:,:,0]**2 + \
# DD[:,:,1]**2 + DD[:,:,2]**2)
# # excitation from bra and ket
# tst0 = numpy.dot(dabs, numpy.dot(tst0,dabs))
#
# numpy.testing.assert_almost_equal(rho0.data, tst0)
def test_get_temperature(self):
"""(Aggregate) Testing temperature retrieval
"""
agg = self.agg
T = agg.get_temperature()
numpy.testing.assert_almost_equal(T, 300.0)
def test_init_coupling_matrix(self):
"""(Aggregate) Testing coupling matrix initialization
"""
agg = TestAggregate(name="dimer-2-env")
self.assertFalse(agg.coupling_initiated)
agg.init_coupling_matrix()
self.assertTrue(agg.coupling_initiated)
self.assertAlmostEqual(0.0, agg.resonance_coupling[0, 1])
def test_set_resonance_coupling(self):
"""(Aggregate) Testing resonance coupling setting with different units
"""
agg = TestAggregate(name="dimer-2-env")
agg.init_coupling_matrix()
agg.set_resonance_coupling(0, 1, 1.0)
self.assertAlmostEqual(1.0, agg.resonance_coupling[0, 1])
self.assertAlmostEqual(1.0, agg.resonance_coupling[1, 0])
with qr.energy_units("1/cm"):
agg.set_resonance_coupling(0, 1, 100.0)
self.assertAlmostEqual(qr.convert(100.0, "1/cm", "int"),
agg.resonance_coupling[0, 1])
self.assertAlmostEqual(qr.convert(100.0, "1/cm", "int"),
agg.resonance_coupling[1, 0])
def test_get_resonance_coupling(self):
"""(Aggregate) Testing resonance coupling retrieval in different units
"""
agg = TestAggregate(name="dimer-2-env")
agg.init_coupling_matrix()
agg.set_resonance_coupling(0, 1, 1.0)
coup = agg.get_resonance_coupling(1, 0)
self.assertAlmostEqual(coup, 1.0)
with qr.energy_units("1/cm"):
coup = agg.get_resonance_coupling(1, 0)
self.assertAlmostEqual(coup, qr.convert(1.0, "int", "1/cm"))
with qr.energy_units("eV"):
coup = agg.get_resonance_coupling(1, 0)
self.assertAlmostEqual(coup, qr.convert(1.0, "int", "eV"))
with qr.energy_units("THz"):
coup = agg.get_resonance_coupling(1, 0)
self.assertAlmostEqual(coup, qr.convert(1.0, "int", "THz"))
def test_set_resonance_coupling_matrix(self):
"""(Aggregate) Testing setting the whole resonance coupling matrix
"""
agg = TestAggregate(name="dimer-2-env")
mat = [[0.0, 1.0], [1.0, 0.0]]
agg.set_resonance_coupling_matrix(mat)
self.assertAlmostEqual(agg.resonance_coupling[1, 0], 1.0)
self.assertAlmostEqual(agg.resonance_coupling[0, 1], 1.0)
self.assertAlmostEqual(agg.resonance_coupling[0, 0], 0.0)
self.assertAlmostEqual(agg.resonance_coupling[1, 1], 0.0)
mat = ((0.0, 500.0), (500.0, 0.0))
with qr.energy_units("1/cm"):
agg.set_resonance_coupling_matrix(mat)
inint = qr.convert(500, "1/cm", "int")
self.assertAlmostEqual(agg.resonance_coupling[1, 0], inint)
self.assertAlmostEqual(agg.resonance_coupling[0, 1], inint)
self.assertAlmostEqual(agg.resonance_coupling[0, 0], 0.0)
self.assertAlmostEqual(agg.resonance_coupling[1, 1], 0.0)
def test_dipole_dipole_coupling(self):
"""(Aggregate) Testing dipole-dipole coupling calculation
"""
agg = TestAggregate(name="dimer-2-env")
coup1 = agg.dipole_dipole_coupling(0, 1)
coup2 = agg.dipole_dipole_coupling(0, 1, epsr=2.0)
self.assertAlmostEqual(coup1, coup2 * 2.0)
with qr.energy_units("1/cm"):
coup = agg.dipole_dipole_coupling(0, 1)
self.assertAlmostEqual(qr.convert(coup1, "int", "1/cm"), coup)
def test_set_coupling_by_dipole_dipole(self):
"""(Aggregate) Testing dipole-dipole coupling calculation for the whole agregate
"""
agg = TestAggregate(name="dimer-2-env")
agg.set_coupling_by_dipole_dipole()
coup1 = agg.dipole_dipole_coupling(0, 1)
self.assertAlmostEqual(coup1, agg.resonance_coupling[0, 1])
with qr.energy_units("1/cm"):
agg.set_coupling_by_dipole_dipole()
coup1 = agg.dipole_dipole_coupling(0, 1)
self.assertAlmostEqual(coup1, agg.resonance_coupling[0, 1])
def test_calculate_resonance_coupling(self):
"""(Aggregate) Testing resonance coupling calculation by various methods
"""
agg = TestAggregate(name="dimer-2-env")
agg.calculate_resonance_coupling(method="dipole-dipole")
coup1 = agg.dipole_dipole_coupling(0, 1)
self.assertEqual(coup1, agg.resonance_coupling[1, 0])
with qr.energy_units("1/cm"):
agg.calculate_resonance_coupling(method="dipole-dipole")
self.assertEqual(coup1, agg.resonance_coupling[1, 0])
def test_add_Molecule(self):
"""(Aggregate) Testing add_Molecule() method
"""
agg = TestAggregate(name="dimer-2-env")
mol = qr.Molecule(elenergies=[0.0, 1.0])
nmols1 = agg.nmono
agg.add_Molecule(mol)
nmols2 = agg.nmono
self.assertEqual(nmols1 + 1, nmols2)
self.assertEqual(len(agg.monomers), nmols2)
self.assertLessEqual(len(agg.mnames), nmols2)
# -*- coding: utf-8 -*-
_show_plots_ = False
from quantarhei import Molecule, Aggregate
#from quantarhei import energy_units
en = [0.0, 1.0]
m1 = Molecule(name="Mol1", elenergies=en)
m2 = Molecule(name="Mol2", elenergies=en)
ag = Aggregate(name="Homodimer")
ag.add_Molecule(m1)
ag.add_Molecule(m2)
ag.set_resonance_coupling(0, 1, 0.1)
ag.build(mult=1)
H = ag.get_Hamiltonian()
#with energy_units("1/cm"):
# print(H)
def redfield_relaxation(self):
print("Redfield rate calculation")
#
# Correlation function
#
params = {
"ftype": world.ctype,
"reorg": world.reorg,
"cortime": world.ctime,
"T": world.temp,
"matsubara": world.mats
}
# FIXME: also time_units, temperature_units
with energy_units(world.e_units):
cf = CorrelationFunction(world.ta, params)
#
# Homodimer
#
with energy_units(world.h_units):
en = world.senergy
m1 = Molecule([0.0, en], "mol1")
m2 = Molecule([0.0, en], "mol2")
# m3 = Molecule("mol2", [0.0, en])
m1.set_egcf((0, 1), cf)
m2.set_egcf((0, 1), cf)
# m3.set_egcf((0,1), cf)
agg = Aggregate(name="Homodimer")
agg.add_Molecule(m1)
agg.add_Molecule(m2)
# agg.add_Molecule(m3)
# with energy_units("1/cm"):
# Hm = m1.get_Hamiltonian()
# print(Hm)
# print(m.convert_energy_2_current_u(Hm._data))
with energy_units(world.r_units):
agg.set_resonance_coupling(0, 1, world.r_coupl)
# agg.set_resonance_coupling(1,2,world.r_coupl)
agg.build()
H = agg.get_Hamiltonian()
# with energy_units("1/cm"):
# print(H)
# print(m.convert_energy_2_current_u(H._data))
sbi = agg.get_SystemBathInteraction()
RRM = RedfieldRateMatrix(H, sbi)
world.K12 = numpy.real(RRM.data[1, 2])
dim = H.dim
rates_M = numpy.zeros(dim * dim)
k = 0
for i in range(dim):
for j in range(dim):
rates_M[k] = RRM.data[i, j]
k += 1
world.rates_M = rates_M
# Molecular dimer without vibrations # from quantarhei import Aggregate mol1 = Molecule(name="Mol 1", elenergies=[0.0, 1.0]) mol2 = Molecule(name="Mol 2", elenergies=[0.0, 1.0]) agg = Aggregate(name="Dimer") agg.add_Molecule(mol1) agg.add_Molecule(mol2) agg.set_resonance_coupling(0,1,0.01) agg.build() H = agg.get_Hamiltonian() print(H) psi = StateVector(3) psi.data[2] = 1.0 dimer_propagator = StateVectorPropagator(time, H) psi_t = dimer_propagator.propagate(psi) psi_t.plot(ptype="square", show=False) #dat = [[0.0, 0.0, 0.0], [0.0, 1.0, 0.01], [0.0, 0.01, 1.1]] H._data[2,2] = 1.2 #dat print(H.data)
#plt.savefig('L12per_pbl_spec.pdf')
plt.show()
with energy_units("1/cm"):
aAnth.plot(axis=[10000,15000,0.0,1.1])
# Redfield Tensor
print("Calculating relaxation tensor ...")
start = tm.time()
# System bath interaction
#sbi = AG.get_system_bath_coupling()
sbi = AG.get_SystemBathInteraction()
# Hamiltonian
HH = AG.get_Hamiltonian()
# Relaxation tensor
RT = RedfieldRelaxationTensor(HH,sbi)
#RT = TDRedfieldRelaxationTensor(HH,sbi)
RT.secularize()
print("... done in ",tm.time()-start)
#for n in range(4):
# print(numpy.real(RT.data[n,n,5,5]))
#
#RR = RedfieldRateMatrix(HH,sbi)
#for n in range(4):
# print(numpy.real(RR.data[n,5]))
"""
m1 = Molecule([0.0, 1.0]) m2 = Molecule([0.0, 1.1]) m3 = Molecule([0.0, 1.2]) from quantarhei import Aggregate agg = Aggregate([m1, m2, m3]) agg.build() # # Operator describing relaxation # from quantarhei.qm import Operator HH = agg.get_Hamiltonian() K = Operator(dim=HH.dim,real=True) K.data[1,2] = 1.0 # # System bath interaction with prescribed rate # from quantarhei.qm import SystemBathInteraction sbi = SystemBathInteraction(sys_operators=[K], rates=(1.0/100,)) agg.set_SystemBathInteraction(sbi) # # Corresponding Lindblad form # from quantarhei.qm import LindbladForm
def redfield_relaxation(self):
print("Redfield rate calculation")
#
# Correlation function
#
params = {"ftype": world.ctype,
"reorg": world.reorg,
"cortime": world.ctime,
"T": world.temp,
"matsubara":world.mats}
# FIXME: also time_units, temperature_units
with energy_units(world.e_units):
cf = CorrelationFunction(world.ta,params)
#
# Homodimer
#
with energy_units(world.h_units):
en = world.senergy
m1 = Molecule([0.0, en],"mol1")
m2 = Molecule([0.0, en], "mol2")
# m3 = Molecule("mol2", [0.0, en])
m1.set_egcf((0,1), cf)
m2.set_egcf((0,1), cf)
# m3.set_egcf((0,1), cf)
agg = Aggregate(name="Homodimer")
agg.add_Molecule(m1)
agg.add_Molecule(m2)
# agg.add_Molecule(m3)
# with energy_units("1/cm"):
# Hm = m1.get_Hamiltonian()
# print(Hm)
# print(m.convert_energy_2_current_u(Hm._data))
with energy_units(world.r_units):
agg.set_resonance_coupling(0,1,world.r_coupl)
# agg.set_resonance_coupling(1,2,world.r_coupl)
agg.build()
H = agg.get_Hamiltonian()
# with energy_units("1/cm"):
# print(H)
# print(m.convert_energy_2_current_u(H._data))
sbi = agg.get_SystemBathInteraction()
RRM = RedfieldRateMatrix(H, sbi)
world.K12 = numpy.real(RRM.data[1,2])
dim = H.dim
rates_M = numpy.zeros(dim*dim)
k = 0
for i in range(dim):
for j in range(dim):
rates_M[k] = RRM.data[i,j]
k += 1
world.rates_M = rates_M
def redfield_tensor(self):
print("Redfield tensor calculation")
#
# Correlation function
#
params = {
"ftype": world.ctype,
"reorg": world.reorg,
"cortime": world.ctime,
"T": world.temp,
"matsubara": world.mats
}
# FIXME: also time_units, temperature_units
with energy_units(world.e_units):
cf = CorrelationFunction(world.ta, params)
#
# Homodimer
#
with energy_units(world.h_units):
en = world.senergy
m1 = Molecule("mol1", [0.0, en])
m2 = Molecule("mol2", [0.0, en])
m1.set_egcf((0, 1), cf)
m2.set_egcf((0, 1), cf)
agg = Aggregate("Homodimer")
agg.add_Molecule(m1)
agg.add_Molecule(m2)
# m = Manager()
##
# with energy_units("1/cm"):
# Hm = m1.get_Hamiltonian()
# print(Hm)
# print(m.convert_energy_2_current_u(Hm._data))
with energy_units(world.r_units):
agg.set_resonance_coupling(0, 1, world.r_coupl)
agg.build()
H = agg.get_Hamiltonian()
world.HH = H
##
# with energy_units("1/cm"):
# print(H)
# print(m.convert_energy_2_current_u(H._data))
sbi = agg.get_SystemBathInteraction()
H.protect_basis()
with eigenbasis_of(H):
RRT = RedfieldRelaxationTensor(H, sbi)
dim = H.dim
rates_T = numpy.zeros(dim * dim)
k = 0
world.K12 = numpy.real(RRT.data[1, 1, 2, 2])
for i in range(dim):
for j in range(dim):
rates_T[k] = numpy.real(RRT.data[i, i, j, j])
k += 1
world.rates_T = rates_T
class AggregateTest(unittest.TestCase):
"""Tests for the Manager class
"""
def setUp(self):
m1 = Molecule(name="Molecule 1", elenergies=[0.0, 1.0])
m2 = Molecule(name="Molecule 2", elenergies=[0.0, 1.0])
time = TimeAxis(0.0, 1000, 1.0)
params = dict(ftype="OverdampedBrownian", reorg=20, cortime=100, T=300)
with energy_units("1/cm"):
fc = CorrelationFunction(time, params)
m1.set_transition_environment((0,1), fc)
m1.position = [0.0, 0.0, 0.0]
m1.set_dipole(0,1,[10.0, 0.0, 0.0])
m2.set_transition_environment((0,1), fc)
m2.position = [10.0, 0.0, 0.0]
m2.set_dipole(0,1,[10.0, 0.0, 0.0])
self.agg = Aggregate(name="TestAgg", molecules=[m1,m2])
self.agg.set_coupling_by_dipole_dipole()
self.agg.build()
m3 = Molecule(name="Molecule 1", elenergies=[0.0, 1.0])
m4 = Molecule(name="Molecule 2", elenergies=[0.0, 1.0])
m3.add_Mode(Mode(0.01))
m4.add_Mode(Mode(0.01))
mod3 = m3.get_Mode(0)
mod4 = m4.get_Mode(0)
mod3.set_nmax(0, 4)
mod3.set_nmax(1, 4)
mod3.set_HR(1, 0.1)
mod4.set_nmax(0, 4)
mod4.set_nmax(1, 4)
mod4.set_HR(1, 0.3)
self.vagg = Aggregate(molecules=[m3, m4])
self.vagg.build()
#########################################################################
#
# TESTS
#
#########################################################################
def test_saving_of_aggregate(self):
"""(Aggregate) Testing its saving capability
"""
use_temporary_file = True
if use_temporary_file:
#drv = "core"
#bcs = False
#with h5py.File('tempfile.hdf5',
# driver=drv,
# backing_store=bcs) as f:
with tempfile.TemporaryFile() as f:
self.agg.save(f, test=True) #,report_unsaved=True)
# reread it
agg = Aggregate()
agg = agg.load(f, test=True)
else:
#with h5py.File('tempfile.hdf5') as f:
with open('tempfile.qrp','wb') as f:
self.agg.save(f)
#with h5py.File('tempfile.hdf5') as f:
with open('tempfile.qrp','rb') as f:
agg = Aggregate()
agg.load(f)
self.assertEqual(self.agg.nmono, agg.nmono)
self.assertEqual(self.agg.mult, agg.mult)
self.assertEqual(self.agg.sbi_mult, agg.sbi_mult)
self.assertEqual(self.agg.name, agg.name)
self.assertEqual(self.agg._has_egcf_matrix, agg._has_egcf_matrix)
self.assertEqual(self.agg._has_system_bath_interaction,
agg._has_system_bath_interaction)
self.assertEqual(self.agg.coupling_initiated, agg.coupling_initiated)
self.assertEqual(self.agg._has_relaxation_tensor,
agg._has_relaxation_tensor)
self.assertEqual(self.agg._relaxation_theory, agg._relaxation_theory)
self.assertEqual(self.agg._built, agg._built)
self.assertEqual(self.agg.Nel,agg.Nel)
self.assertEqual(self.agg.Ntot,agg.Ntot)
numpy.testing.assert_array_equal(self.agg.Nb,agg.Nb)
for key in agg.mnames.keys():
self.assertEqual(self.agg.mnames[key],agg.mnames[key])
numpy.testing.assert_array_equal(self.agg.resonance_coupling,
agg.resonance_coupling)
mnames = ["Molecule 1", "Molecule 2"]
for k in range(agg.nmono):
m = agg.monomers[k]
self.assertIn(m.name, mnames)
mnames.remove(m.name)
def test_trace_over_vibrations(self):
"""(Aggregate) Testing trace over vibrational DOF
"""
agg = self.vagg
ham = agg.get_Hamiltonian()
rho = ReducedDensityMatrix(dim=ham.dim)
rho._data[5, 5] = 1.0
redr = agg.trace_over_vibrations(rho)
numpy.testing.assert_almost_equal(numpy.trace(redr._data), 1.0,
decimal=7)
N = agg.Nb[0]
rho = ReducedDensityMatrix(dim=ham.dim)
rho._data[N+5, N+5] = 1.0
redr = agg.trace_over_vibrations(rho)
numpy.testing.assert_almost_equal(numpy.trace(redr._data), 1.0,
decimal=3)
N = agg.Nb[1]
rho = ReducedDensityMatrix(dim=ham.dim)
rho._data[N+5, N+5] = 1.0
redr = agg.trace_over_vibrations(rho)
numpy.testing.assert_almost_equal(numpy.trace(redr._data), 1.0,
decimal=2)
def test_get_Density_Matrix_thermal(self):
"""(Aggregate) Testing the get_Densitymatrix method with `thermal` condition type
"""
from quantarhei.core.units import kB_intK
vagg = self.vagg
H = vagg.get_Hamiltonian()
N = H.data.shape[0]
# zero temperature
rho0 = vagg.get_DensityMatrix(condition_type="thermal")
tst0 = numpy.zeros((N,N),dtype=qr.COMPLEX)
tst0[0,0] = 1.0
numpy.testing.assert_almost_equal(rho0.data, tst0)
# room temperature
rho0 = vagg.get_DensityMatrix(condition_type="thermal",
temperature=300)
# cannonical balance between neighboring states is tested
kbT = kB_intK*300.0
for k in range(N-1):
E2 = H.data[k+1,k+1]
E1 = H.data[k,k]
ratio = numpy.exp(-(E2-E1)/kbT)
numpy.testing.assert_almost_equal(ratio,
rho0.data[k+1,k+1]/rho0.data[k,k])
def test_get_Density_Matrix_thermal_excited(self):
"""(Aggregate) Testing the get_Densitymatrix method with `thermal_excited_state` condition type
"""
from quantarhei.core.units import kB_intK
vagg = self.vagg
H = vagg.get_Hamiltonian()
N = H.data.shape[0]
Nb0 = vagg.Nb[0]
# zero temperature
rho0 = vagg.get_DensityMatrix(condition_type="thermal_excited_state")
tst0 = numpy.zeros((N,N),dtype=qr.COMPLEX)
tst0[Nb0,Nb0] = 1.0
numpy.testing.assert_almost_equal(rho0.data, tst0)
# room temperature
kbT = kB_intK*300.0
H = self.agg.get_Hamiltonian()
N = H.data.shape[0]
Nb0 = self.agg.Nb[0]
with qr.eigenbasis_of(H):
rho0 = self.agg.get_DensityMatrix(condition_type="thermal_excited_state",
temperature=300)
tst0 = numpy.zeros((N,N),dtype=qr.COMPLEX)
with qr.eigenbasis_of(H):
ssum = 0.0
for i in range(Nb0, N):
tst0[i,i] = numpy.exp(-(H.data[i,i]-H.data[Nb0,Nb0])/kbT)
ssum += tst0[i,i]
tst0 = tst0/ssum
numpy.testing.assert_almost_equal(rho0.data, tst0)
# ssum = 0.0
# for i in range(N):
# tst0[i,i] = numpy.exp(-H.data[i,i]/kbT)
# ssum += tst0[i,i]
# tst0 = tst0/ssum
#
# DD = vagg.TrDMOp.data
# # abs value of the transition dipole moment
# dabs = numpy.sqrt(DD[:,:,0]**2 + \
# DD[:,:,1]**2 + DD[:,:,2]**2)
# # excitation from bra and ket
# tst0 = numpy.dot(dabs, numpy.dot(tst0,dabs))
#
# numpy.testing.assert_almost_equal(rho0.data, tst0)
def test_get_temperature(self):
"""(Aggregate) Testing temperature retrieval
"""
agg = self.agg
T = agg.get_temperature()
numpy.testing.assert_almost_equal(T, 300.0)
def test_init_coupling_matrix(self):
"""(Aggregate) Testing coupling matrix initialization
"""
agg = TestAggregate(name="dimer-2-env")
self.assertFalse(agg.coupling_initiated)
agg.init_coupling_matrix()
self.assertTrue(agg.coupling_initiated)
self.assertAlmostEqual(0.0, agg.resonance_coupling[0,1])
def test_set_resonance_coupling(self):
"""(Aggregate) Testing resonance coupling setting with different units
"""
agg = TestAggregate(name="dimer-2-env")
agg.init_coupling_matrix()
agg.set_resonance_coupling(0, 1, 1.0)
self.assertAlmostEqual(1.0, agg.resonance_coupling[0,1])
self.assertAlmostEqual(1.0, agg.resonance_coupling[1,0])
with qr.energy_units("1/cm"):
agg.set_resonance_coupling(0, 1, 100.0)
self.assertAlmostEqual(qr.convert(100.0, "1/cm", "int"),
agg.resonance_coupling[0,1])
self.assertAlmostEqual(qr.convert(100.0, "1/cm", "int"),
agg.resonance_coupling[1,0])
def test_get_resonance_coupling(self):
"""(Aggregate) Testing resonance coupling retrieval in different units
"""
agg = TestAggregate(name="dimer-2-env")
agg.init_coupling_matrix()
agg.set_resonance_coupling(0, 1, 1.0)
coup = agg.get_resonance_coupling(1,0)
self.assertAlmostEqual(coup, 1.0)
with qr.energy_units("1/cm"):
coup = agg.get_resonance_coupling(1,0)
self.assertAlmostEqual(coup, qr.convert(1.0, "int", "1/cm"))
with qr.energy_units("eV"):
coup = agg.get_resonance_coupling(1,0)
self.assertAlmostEqual(coup, qr.convert(1.0, "int", "eV"))
with qr.energy_units("THz"):
coup = agg.get_resonance_coupling(1,0)
self.assertAlmostEqual(coup, qr.convert(1.0, "int", "THz"))
def test_set_resonance_coupling_matrix(self):
"""(Aggregate) Testing setting the whole resonance coupling matrix
"""
agg = TestAggregate(name="dimer-2-env")
mat = [[0.0, 1.0],
[1.0, 0.0]]
agg.set_resonance_coupling_matrix(mat)
self.assertAlmostEqual(agg.resonance_coupling[1,0], 1.0)
self.assertAlmostEqual(agg.resonance_coupling[0,1], 1.0)
self.assertAlmostEqual(agg.resonance_coupling[0,0], 0.0)
self.assertAlmostEqual(agg.resonance_coupling[1,1], 0.0)
mat = ((0.0, 500.0),
(500.0, 0.0))
with qr.energy_units("1/cm"):
agg.set_resonance_coupling_matrix(mat)
inint = qr.convert(500, "1/cm", "int")
self.assertAlmostEqual(agg.resonance_coupling[1,0], inint)
self.assertAlmostEqual(agg.resonance_coupling[0,1], inint)
self.assertAlmostEqual(agg.resonance_coupling[0,0], 0.0)
self.assertAlmostEqual(agg.resonance_coupling[1,1], 0.0)
def test_dipole_dipole_coupling(self):
"""(Aggregate) Testing dipole-dipole coupling calculation
"""
agg = TestAggregate(name="dimer-2-env")
coup1 = agg.dipole_dipole_coupling(0,1)
coup2 = agg.dipole_dipole_coupling(0,1, epsr=2.0)
self.assertAlmostEqual(coup1, coup2*2.0)
with qr.energy_units("1/cm"):
coup = agg.dipole_dipole_coupling(0,1)
self.assertAlmostEqual(qr.convert(coup1,"int","1/cm"), coup)
def test_set_coupling_by_dipole_dipole(self):
"""(Aggregate) Testing dipole-dipole coupling calculation for the whole agregate
"""
agg = TestAggregate(name="dimer-2-env")
agg.set_coupling_by_dipole_dipole()
coup1 = agg.dipole_dipole_coupling(0,1)
self.assertAlmostEqual(coup1, agg.resonance_coupling[0,1])
with qr.energy_units("1/cm"):
agg.set_coupling_by_dipole_dipole()
coup1 = agg.dipole_dipole_coupling(0,1)
self.assertAlmostEqual(coup1, agg.resonance_coupling[0,1])
def test_calculate_resonance_coupling(self):
"""(Aggregate) Testing resonance coupling calculation by various methods
"""
agg = TestAggregate(name="dimer-2-env")
agg.calculate_resonance_coupling(method="dipole-dipole")
coup1 = agg.dipole_dipole_coupling(0,1)
self.assertEqual(coup1, agg.resonance_coupling[1,0])
with qr.energy_units("1/cm"):
agg.calculate_resonance_coupling(method="dipole-dipole")
self.assertEqual(coup1, agg.resonance_coupling[1,0])
def test_add_Molecule(self):
"""(Aggregate) Testing add_Molecule() method
"""
agg = TestAggregate(name="dimer-2-env")
mol = qr.Molecule(elenergies=[0.0, 1.0])
nmols1 = agg.nmono
agg.add_Molecule(mol)
nmols2 = agg.nmono
self.assertEqual(nmols1 + 1, nmols2)
self.assertEqual(len(agg.monomers), nmols2)
self.assertLessEqual(len(agg.mnames), nmols2)
m1 = Molecule([0.0, 1.0]) m2 = Molecule([0.0, 1.1]) m3 = Molecule([0.0, 1.2]) from quantarhei import Aggregate agg = Aggregate([m1, m2, m3]) agg.build() # # Operator describing relaxation # from quantarhei.qm import Operator HH = agg.get_Hamiltonian() K = Operator(dim=HH.dim, real=True) K.data[1, 2] = 1.0 # # System bath interaction with prescribed rate # from quantarhei.qm import SystemBathInteraction sbi = SystemBathInteraction(sys_operators=[K], rates=(1.0 / 100, )) agg.set_SystemBathInteraction(sbi) # # Corresponding Lindblad form # from quantarhei.qm import LindbladForm
def redfield_tensor(self):
print("Redfield tensor calculation")
#
# Correlation function
#
params = {"ftype": world.ctype,
"reorg": world.reorg,
"cortime": world.ctime,
"T": world.temp,
"matsubara":world.mats}
# FIXME: also time_units, temperature_units
with energy_units(world.e_units):
cf = CorrelationFunction(world.ta,params)
#
# Homodimer
#
with energy_units(world.h_units):
en = world.senergy
m1 = Molecule([0.0, en], "mol1")
m2 = Molecule([0.0, en], "mol2")
m1.set_egcf((0,1), cf)
m2.set_egcf((0,1), cf)
agg = Aggregate(name="Homodimer")
agg.add_Molecule(m1)
agg.add_Molecule(m2)
# m = Manager()
##
# with energy_units("1/cm"):
# Hm = m1.get_Hamiltonian()
# print(Hm)
# print(m.convert_energy_2_current_u(Hm._data))
with energy_units(world.r_units):
agg.set_resonance_coupling(0,1,world.r_coupl)
agg.build()
H = agg.get_Hamiltonian()
world.HH = H
##
# with energy_units("1/cm"):
# print(H)
# print(m.convert_energy_2_current_u(H._data))
sbi = agg.get_SystemBathInteraction()
H.protect_basis()
with eigenbasis_of(H):
RRT = RedfieldRelaxationTensor(H, sbi)
dim = H.dim
rates_T = numpy.zeros(dim*dim)
k = 0
world.K12 = numpy.real(RRT.data[1,1,2,2])
for i in range(dim):
for j in range(dim):
rates_T[k] = numpy.real(RRT.data[i,i,j,j])
k += 1
world.rates_T = rates_T
