Spectro-temporal symmetry in action-detected optical spectroscopy: Highlighting excited-state dynamics in large systems
The Journal of Chemical Physics,
Journal Year:
2025,
Volume and Issue:
162(12)
Published: March 28, 2025
Multidimensional
optical
spectroscopy
observes
transient
excitation
dynamics
through
time
evolution
of
spectral
correlations.
Its
action-detected
variants
offer
several
advantages
over
the
coherent
detection
and
are
thus
becoming
increasingly
widespread.
Nevertheless,
a
drawback
spectra
is
presence
stationary
background
so-called
incoherent
mixing
excitations
from
independent
states
that
resembles
product
ground-state
absorption
obscures
excited-state
signal.
This
issue
especially
problematic
in
fluorescence-detected
two-dimensional
electronic
(F-2DES)
pump-probe
(F-PP)
extended
systems,
where
large
arises
efficient
exciton-exciton
annihilation.
In
this
work,
we
demonstrate
on
example
F-2DES
F-PP
an
inherent
spectro-temporal
symmetry
spectra,
which
allows
general,
system-independent
subtraction
any
signals
including
mixing.
We
derive
expressions
for
with
normal
reversed
ordering
pulses,
relating
these
to
system
response.
As
show
both
analytically
numerically,
difference
signal
constructed
pulse
free
highlights
dynamics.
further
verify
approach
experimental
molecular
squaraine
heterodimer
photosynthetic
antenna
light-harvesting
complex
2
purple
bacteria.
The
generally
applicable
2DES
without
modifications
studied
system,
enabling
their
application
systems
such
as
complexes.
Language: Английский
Simulating Non-Markovian Dynamics in Multidimensional Electronic Spectroscopy via Quantum Algorithm
Journal of Chemical Theory and Computation,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 25, 2024
Including
the
effect
of
molecular
environment
in
numerical
modeling
time-resolved
electronic
spectroscopy
remains
an
important
challenge
computational
spectroscopy.
In
this
contribution,
we
present
a
general
approach
for
simulation
optical
response
multichromophore
systems
structured
and
its
implementation
as
quantum
algorithm.
A
key
step
procedure
is
pseudomode
embedding
system-environment
problem
resulting
finite
set
states
evolving
according
to
Markovian
master
equation.
This
formulation
then
solved
by
collision
model
integrated
into
algorithm
designed
simulate
linear
nonlinear
functions.
The
workflow
validated
simulating
spectra
prototypical
excitonic
dimer
interacting
with
fast
(memoryless)
finite-memory
environments.
results
demonstrate,
on
one
hand,
potential
dynamical
features
spectroscopy,
including
lineshape,
spectral
diffusion,
relaxations
along
delay
times.
On
other
explicit
synthesis
circuits
provides
fully
protocol
harnessing
efficient
many-body
dynamics
promised
future
generation
fault-tolerant
computers.
Language: Английский