Stochastic resonance in vibrational polariton chemistry
The Journal of Chemical Physics,
Journal Year:
2025,
Volume and Issue:
162(6)
Published: Feb. 10, 2025
In
this
work,
we
systematically
investigate
the
impact
of
ambient
noise
intensity
on
rate
modifications
ground-state
chemical
reactions
in
an
optical
cavity
under
vibrational
strong-coupling
conditions.
To
achieve
this,
utilize
a
numerically
exact
open
quantum
system
approach—the
hierarchical
equations
motion
twin
space,
combined
with
flexible
tree
tensor
network
state
solver.
Our
findings
reveal
stochastic
resonance
phenomenon
cavity-modified
reactivities:
optimal
reaction
enhancement
occurs
at
intermediate
level.
other
words,
diminishes
if
noise,
sensed
by
cavity–molecule
through
leakage,
is
either
too
weak
or
excessively
strong.
collective
coupling
regime,
when
weakly
damped,
strengthens
as
more
molecules
couple
to
cavity.
contrast,
strong
damping,
rates
decline
number
grows.
Language: Английский
Quantum nature of reactivity modification in vibrational polariton chemistry
The Journal of Chemical Physics,
Journal Year:
2024,
Volume and Issue:
161(5)
Published: Aug. 1, 2024
In
this
work,
we
present
a
mixed
quantum–classical
open
quantum
system
dynamics
method
for
studying
rate
modifications
of
ground-state
chemical
reactions
in
an
optical
cavity
under
vibrational
strong-coupling
conditions.
approach,
the
radiation
mode
is
treated
classically
with
mean-field
nuclear
force
averaging
over
remaining
degrees
freedom,
both
within
and
environment,
which
are
handled
mechanically
hierarchical
equations
motion
framework.
Using
conduct
comparative
analysis
by
juxtaposing
results
fully
quantum-mechanical
simulations.
After
eliminating
spurious
peaks
that
can
occur
when
not
using
rigorous
definition
constant,
confirm
crucial
role
nature
reproducing
resonant
peak
observed
frequency-dependent
profile.
other
words,
it
appears
necessary
to
explicitly
consider
quantized
photonic
states
reactivity
modification
polariton
chemistry
(at
least
model
systems
studied
work),
as
these
phenomena
stem
from
cavity-induced
reaction
pathways
involving
energy
exchanges
between
photons
molecular
transitions.
Language: Английский
Cavity induced modulation of intramolecular vibrational energy flow pathways
The Journal of Chemical Physics,
Journal Year:
2024,
Volume and Issue:
161(19)
Published: Nov. 15, 2024
Recent
experiments
in
polariton
chemistry
indicate
that
reaction
rates
can
be
significantly
enhanced
or
suppressed
inside
an
optical
cavity.
One
possible
explanation
for
the
rate
modulation
involves
cavity
mode
altering
intramolecular
vibrational
energy
redistribution
(IVR)
pathways
by
coupling
to
specific
molecular
vibrations
strong
(VSC)
regime.
However,
mechanism
such
a
cavity-mediated
of
IVR
is
yet
understood.
In
recent
study,
Ahn
et
al.
[Science
380,
1165
(2023)]
observed
alcoholysis
phenyl
isocyanate
(PHI)
considerably
when
tuned
resonant
with
(NCO)
stretching
PHI.
Here,
we
analyze
quantum
and
classical
dynamics
model
effective
Hamiltonian
PHI
involving
high-frequency
NCO-stretch
two
key
low-frequency
ring
modes.
We
compute
various
indicators
extent
cavity–molecule
system
show
tuning
frequency
NCO-stretching
strongly
perturbs
cavity-free
pathways.
Subsequent
anharmonic
resonances
lead
efficient
scrambling
initial
overtone
state
over
number
space.
also
hybrid
light–matter
states
undergo
localization–delocalization
transition
VSC
Language: Английский
Cavity-modified local and non-local electronic interactions in molecular ensembles under vibrational strong coupling
The Journal of Chemical Physics,
Journal Year:
2024,
Volume and Issue:
161(16)
Published: Oct. 25, 2024
Resonant
vibrational
strong
coupling
(VSC)
between
molecular
vibrations
and
quantized
field
modes
of
low-frequency
optical
cavities
constitutes
the
conceptual
cornerstone
vibro-polaritonic
chemistry.
In
this
work,
we
theoretically
investigate
role
complementary
nonresonant
electron-photon
interactions
in
cavity
Born-Oppenheimer
(CBO)
approximation.
particular,
study
cavity-induced
modifications
local
non-local
electronic
dipole-coupled
ensembles
under
VSC.
Methodologically,
combine
CBO
perturbation
theory
(CBO-PT)
[E.
W.
Fischer
P.
Saalfrank,
J.
Chem.
Theory
Comput.
19,
7215
(2023)]
with
non-perturbative
Hartree-Fock
(HF)
coupled
cluster
(CC)
theories.
a
first
step,
derive
up
to
second-order
CBO-PT
potential
energy
surfaces,
which
reveal
non-trivial
intra-
inter-molecular
corrections
induced
by
cavity.
We
then
introduce
concept
reaction
(CRP),
minimizing
subspace
discuss
mechanisms.
present
reformulations
CBO-HF
CBO-CC
approaches
for
CRPs
approximate
from
unimolecular
bimolecular
scenarios.
case,
find
small
surfaces
selected
isomerization
reactions
dominantly
captured
first-order
dipole
fluctuation
correction.
Excellent
agreement
wave
function
results
indicates
minor
VSC-induced
state
relaxation
effects
single-molecule
limit.
scenario,
reveals
an
explicit
interacting
dimers
besides
cavity-polarization
dependent
dipole-induced
van
der
Waals
enhanced
long-range
character.
An
illustrative
CBO-coupled
singles
doubles-based
numerical
analysis
dimer
models
provides
perspective
on
cavity-modified
intermolecular
Language: Английский
A theoretical chemistry approach to vibro-polaritonic chemistry with application to infrared spectroscopy and reaction kinetics
Chemical modelling,
Journal Year:
2024,
Volume and Issue:
unknown, P. 137 - 160
Published: Dec. 20, 2024
The
emerging
interdisciplinary
research
field
of
vibro-polaritonic
chemistry
exploits
the
concept
vibrational
strong
coupling
(VSC)
to
shape
chemical
reactivity
and
molecular
properties.
Vibro-polaritonic
employs
optical
Fabry–Pérot
cavities
as
a
novel
light
source,
which
provide
access
VSC
between
confined
infrared
(IR)
radiation
modes
(ro)vibrational
degrees
freedom.
induces
formation
light–matter
hybrid
states
known
polaritons,
are
experimentally
characterized
by
paradigmatic
doublet
signature
in
linear
IR
spectra.
Mechanistically
even
more
intriguing
is
reported
observation
VSC-modified
ground
state
chemistry.
From
conceptual
perspective,
differs
from
traditional
laser-based
interaction
scenarios:
While
latter
commonly
rely
on
semiclassical
approach
subject
classical
description
electromagnetic
field,
entire
system
described
quantum
mechanically.
This
chapter
provides
contemporary
overview
perspective
theoretical
chemist.
Theoretical
concepts
extending
common
towards
interactions
with
quantized
cavity
fields
presented
an
introductory
fashion.
Applications
spectroscopy
reaction
kinetics
regime
illustratively
discussed
for
selected
model
problems.
Language: Английский