Stochastic resonance in vibrational polariton chemistry
The Journal of Chemical Physics,
Год журнала:
2025,
Номер
162(6)
Опубликована: Фев. 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.
Язык: Английский
Exact factorization of the photon–electron–nuclear wavefunction: Formulation and coupled-trajectory dynamics
The Journal of Chemical Physics,
Год журнала:
2024,
Номер
161(8)
Опубликована: Авг. 27, 2024
We
employ
the
exact-factorization
formalism
to
study
coupled
dynamics
of
photons,
electrons,
and
nuclei
at
quantum
mechanical
level,
proposing
illustrative
examples
model
situations
nonadiabatic
spontaneous
emission
electron–nuclear
systems
in
regime
strong
light–matter
coupling.
make
a
particular
choice
factorization
for
such
multi-component
system,
where
full
wavefunction
is
factored
as
conditional
electronic
amplitude
marginal
photon–nuclear
amplitude.
Then,
we
apply
coupled-trajectory
mixed
quantum–classical
(CTMQC)
algorithm
perform
trajectory-based
simulations,
by
treating
photonic
nuclear
degrees
freedom
on
equal
footing
terms
classical-like
trajectories.
The
analysis
time-dependent
potentials
theory
along
with
assessment
performance
CTMQC
allows
us
point
out
some
limitations
current
approximations
used
CTMQC.
Meanwhile,
comparing
other
algorithms,
namely
multi-trajectory
Ehrenfest
Tully
surface
hopping,
demonstrates
better
quality
predictions.
Язык: Английский
Cavity induced modulation of intramolecular vibrational energy flow pathways
The Journal of Chemical Physics,
Год журнала:
2024,
Номер
161(19)
Опубликована: Ноя. 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
Язык: Английский