We
applied
a
variety
of
mixed
quantum-classical
(MQC)
approaches
to
simulate
the
VSC-influenced
reaction
rate
constant.
All
these
MQC
simulations
treat
key
vibrational
levels
associated
with
coordinate
in
quantum
subsystem
(as
states),
whereas
all
other
degrees
freedom
(DOFs)
are
treated
inside
classical
subsystem.
find
that
as
long
we
have
state
descriptions
for
DOFs,
one
can
correctly
describe
VSC
resonance
condition
when
cavity
frequency
matches
bond
frequency.
This
correct
behavior
be
obtained
regardless
detailed
methods
uses.
The
results
suggest
generate
semi-quantitative
agreement
exact
constant
changes
changing
frequency,
light-matter
coupling
strength,
or
lifetime.
finding
this
work
suggests
use
computationally
economic
explore
collective
scenario
many
molecules
collectively
coupled
modes
future.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(8), P. 5402 - 5413
Published: Feb. 14, 2024
Altering
chemical
reactivity
and
material
structure
in
confined
optical
environments
is
on
the
rise,
yet,
a
conclusive
understanding
of
microscopic
mechanisms
remains
elusive.
This
originates
mostly
from
fact
that
accurately
predicting
vibrational
reactive
dynamics
for
soluted
ensembles
realistic
molecules
no
small
endeavor,
adding
(collective)
strong
light–matter
interaction
does
not
simplify
matters.
Here,
we
establish
framework
based
combination
machine
learning
(ML)
models,
trained
using
density-functional
theory
calculations
molecular
to
accelerate
such
simulations.
We
then
apply
this
approach
evaluate
coupling,
changes
reaction
rate
constant,
their
influence
enthalpy
entropy
deprotection
1-phenyl-2-trimethylsilylacetylene,
which
has
been
studied
previously
both
experimentally
ab
initio
While
find
qualitative
agreement
with
critical
experimental
observations,
especially
regard
kinetics,
also
differences
comparison
previous
theoretical
predictions.
The
features
ML-accelerated
simulations
agree
show
estimated
kinetic
behavior.
Conflicting
indicate
contribution
dynamic
electronic
polarization
process
more
relevant
than
currently
believed.
Our
work
demonstrates
practical
use
ML
polaritonic
chemistry,
discusses
limitations
common
approximations,
paves
way
holistic
description
chemistry.
The Journal of Chemical Physics,
Journal Year:
2023,
Volume and Issue:
159(8)
Published: Aug. 22, 2023
We
present
numerically
exact
quantum
dynamics
simulations
using
the
hierarchical
equation
of
motion
approach
to
investigate
resonance
enhancement
chemical
reactions
due
vibrational
strong
coupling
(VSC)
in
polariton
chemistry.
The
results
reveal
that
cavity
mode
acts
like
a
“rate-promoting
mode”
enhances
ground
state
reaction
rate
constant
when
frequency
matches
transition
frequency.
simulation
predicts
VSC-modified
will
change
quadratically
as
light–matter
strength
increases.
When
changing
lifetime
from
lossy
limit
lossless
limit,
predict
there
be
turnover
constant.
Based
on
numerical
observations,
we
an
analytic
theory
explain
observed
sharp
peak
profile
tuning
match
excited
states.
This
further
explains
origin
broadening
profile.
agrees
with
under
golden
rule
and
short
limit.
To
best
our
knowledge,
this
is
first
able
behavior
adiabatic
cavity.
envision
both
analysis
offer
invaluable
theoretical
insights
into
fundamental
mechanism
VSC-induced
modifications
The Journal of Chemical Physics,
Journal Year:
2024,
Volume and Issue:
160(18)
Published: May 8, 2024
Experiments
have
demonstrated
that
vibrational
strong
coupling
between
molecular
vibrations
and
light
modes
can
significantly
change
properties,
such
as
ground-state
reactivity.
Theoretical
studies
toward
the
origin
of
this
exciting
observation
roughly
be
divided
into
two
categories,
with
based
on
Hamiltonians
simply
couple
a
molecule
to
cavity
mode
via
its
dipole
moment
one
hand,
other
hand
ab
initio
calculations
self-consistently
include
effect
electronic
ground
state
within
Born-Oppenheimer
(CBO)
approximation;
these
approaches
are
not
equivalent.
The
CBO
approach
is
more
rigorous,
but
unfortunately
it
requires
rewriting
electronic-structure
code,
results
may
sometimes
hard
physically
interpret.
In
work,
we
exploit
relation
demonstrate
real
(hydrogen
fluoride)
for
realistic
strengths,
recover
energies
spectra
high
accuracy
using
only
out-of-cavity
quantities
from
standard
calculations.
doing
so,
discover
what
thephysical
effects
underlying
are.
Our
methodology
aid
in
incorporating
possibly
important
features
models,
play
pivotal
role
demystifying
results,
provide
practical
efficient
alternative
full
Nanophotonics,
Journal Year:
2024,
Volume and Issue:
13(14), P. 2601 - 2615
Published: Feb. 23, 2024
We
present
a
theory
that
explains
the
resonance
effect
of
vibrational
strong
coupling
(VSC)
modified
reaction
rate
constant
at
normal
incidence
Fabry-Pérot
(FP)
cavity.
This
analytic
is
based
on
mechanistic
hypothesis
cavity
modes
promote
transition
from
ground
state
to
excited
reactant,
which
rate-limiting
step
reaction.
mechanism
for
single
molecule
coupled
single-mode
has
been
confirmed
by
numerically
exact
simulations
in
our
recent
work
[J.
Chem.
Phys.
159,
084104
(2023)].
Using
Fermi's
golden
rule
(FGR),
we
formulate
this
many
molecules
inside
FP
microcavity.
The
provides
possible
explanation
condition
observed
VSC
and
plausible
why
only
incident
angle
there
effect,
whereas,
an
oblique
incidence,
no
apparent
even
though
both
cases
generate
Rabi
splitting
forming
polariton
states.
On
other
hand,
current
cannot
explain
collective
when
large
number
are
collectively
cavity,
future
required
build
complete
microscopic
all
phenomena
VSC.
Nanophotonics,
Journal Year:
2024,
Volume and Issue:
13(14), P. 2617 - 2633
Published: March 18, 2024
Abstract
In
this
paper,
we
develop
quantum
dynamical
methods
capable
of
treating
the
dynamics
chemically
reacting
systems
in
an
optical
cavity
vibrationally
strong-coupling
(VSC)
limit
at
finite
temperatures
and
presence
a
dissipative
solvent
both
few
many
molecule
limits.
context
two
simple
models,
demonstrate
how
reactivity
collective
VSC
regime
does
not
exhibit
altered
rate
behavior
equilibrium
but
may
resonant
modification
when
system
is
explicitly
out
equilibrium.
Our
results
suggest
experimental
protocols
that
be
used
to
modify
point
features
included
models
studied,
which
demand
further
scrutiny.
The Journal of Chemical Physics,
Journal Year:
2024,
Volume and Issue:
160(17)
Published: May 2, 2024
In
response
to
a
community
prediction
challenge,
we
simulate
the
nonadiabatic
dynamics
of
cyclobutanone
using
mapping
approach
surface
hopping
(MASH).
We
consider
first
500
fs
relaxation
following
photoexcitation
S2
state
and
predict
corresponding
time-resolved
electron-diffraction
signal
that
will
be
measured
by
planned
experiment.
397
ab
initio
trajectories
were
obtained
on
fly
with
state-averaged
complete
active
space
self-consistent
field
(12,11)
space.
To
obtain
an
estimate
potential
systematic
error,
198
calculated
aug-cc-pVDZ
basis
set
199
6-31+G*
set.
MASH
is
recently
proposed
independent
trajectory
method
for
simulating
dynamics,
originally
derived
two-state
problems.
As
there
are
three
relevant
electronic
states
in
this
system,
used
newly
developed
multi-state
generalization
simulation:
uncoupled
spheres
(unSMASH).
This
study,
therefore,
serves
both
as
investigation
photodissociation
cyclobutanone,
also
demonstration
applicability
unSMASH
simulations.
line
previous
experimental
studies,
observe
simulated
dominated
sets
dissociation
products,
C3H6
+
CO,
C2H4
C2H2O,
CH2
interpret
our
predicted
terms
key
features
associated
pathways.
The Journal of Physical Chemistry Letters,
Journal Year:
2023,
Volume and Issue:
14(49), P. 11208 - 11216
Published: Dec. 6, 2023
We
applied
a
variety
of
mixed
quantum-classical
(MQC)
approaches
to
simulate
the
VSC-influenced
reaction
rate
constant.
All
these
MQC
simulations
treat
key
vibrational
levels
associated
with
coordinate
in
quantum
subsystem
(as
states),
whereas
all
other
degrees
freedom
(DOFs)
are
treated
inside
classical
subsystem.
find
that,
as
long
we
have
state
descriptions
for
DOFs,
one
can
correctly
describe
VSC
resonance
condition
when
cavity
frequency
matches
bond
frequency.
This
correct
behavior
be
obtained
regardless
detailed
methods
that
uses.
The
results
suggest
generate
semiquantitative
agreement
exact
constant
changes
changing
frequency,
light-matter
coupling
strength,
or
lifetime.
finding
this
work
suggests
use
computationally
economic
explore
collective
scenario
many
molecules
collectively
coupled
modes
future.
The Journal of Chemical Physics,
Journal Year:
2024,
Volume and Issue:
160(22)
Published: June 10, 2024
In
this
work,
we
systematically
investigate
the
mechanisms
underlying
rate
modification
of
ground-state
chemical
reactions
in
an
optical
cavity
under
vibrational
strong-coupling
conditions.
We
employ
a
symmetric
double-well
description
molecular
potential
energy
surface
and
numerically
exact
open
quantum
system
approach—the
hierarchical
equations
motion
twin
space
with
matrix
product
state
solver.
Our
results
predict
existence
multiple
peaks
photon
frequency-dependent
profile
for
strongly
anharmonic
transition
energies.
The
emergence
new
peak
is
attributed
to
opening
intramolecular
reaction
pathway,
energetically
fueled
by
bath
through
resonant
mode.
intensity
determined
jointly
kinetic
factors.
Going
beyond
single-molecule
limit,
examine
effects
collective
coupling
two
molecules
cavity.
find
that
when
identical
are
simultaneously
coupled
same
mode,
further
increased.
This
additional
increase
associated
activation
cavity-induced
intermolecular
channel.
Furthermore,
due
these
cavity-promoted
pathways
remains
unaffected,
regardless
whether
dipole
moments
aligned
or
opposite
direction
as
light
polarization.
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.
Journal of Chemical Theory and Computation,
Journal Year:
2024,
Volume and Issue:
20(8), P. 3019 - 3027
Published: April 12, 2024
It
has
been
experimentally
demonstrated
that
molecular-vibration
polaritons
formed
by
strong
coupling
of
a
molecular
vibration
to
an
infrared
cavity
mode
can
significantly
modify
the
physical
properties
and
chemical
reactivities
various
systems.
However,
complete
theoretical
understanding
underlying
mechanisms
modifications
remains
elusive
due
complexity
hybrid
system,
especially
collective
nature
polaritonic
states
in
systems
containing
many
molecules.
We
develop
here
semiclassical
theory
vibration-polariton
dynamics
based
on
truncated
Wigner
approximation
(TWA)
is
tractable
large
simultaneously
captures
quantum
character
photons
optical
cavity.
The
then
applied
investigate
nuclear
system
identical
diatomic
molecules
having
ground-state
Morse
potential
being
strongly
coupled
ultrastrong
regime.
validity
TWA
examined
comparing
it
with
full
single-molecule
for
two
different
initial
dipole
Coulomb
gauges.
For
tensor-product
ground
state
gauge,
which
corresponds
light-matter
entangled
resonance
effects
formation
are
observed
