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 Chemical Theory and Computation,
Journal Year:
2024,
Volume and Issue:
20(10), P. 4278 - 4287
Published: May 8, 2024
The
formation
of
molecular
vibrational
polaritons,
arising
from
the
interplay
between
vibrations
and
infrared
cavity
modes,
is
a
quantum
phenomenon
necessitating
accurate
dynamical
simulations.
Here,
we
introduce
self-consistent
field/virtual
state
configuration
interaction
method,
enabling
simulation
spectra
many-molecule
systems
within
optical
cavity.
Focusing
on
representative
(H
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.
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
mechanical
simulations.
Through
comparison,
confirm
crucial
role
nature
reproducing
resonant
peak
observed
frequency-dependent
profile.
other
words,
it
to
explicitly
consider
quantized
photonic
states
reactivity
modification
polariton
chemistry,
as
these
phenomena
stem
from
cavity-induced
reaction
pathways
involving
energy
exchanges
between
photons
molecular
transitions.
The Journal of Chemical Physics,
Journal Year:
2024,
Volume and Issue:
161(8)
Published: Aug. 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.
Physical Chemistry Chemical Physics,
Journal Year:
2024,
Volume and Issue:
26(42), P. 26693 - 26718
Published: Jan. 1, 2024
This
perspective
offers
an
overview
of
the
applications
exact
factorization
electron-nuclear
wavefunction
in
simulations
ultrafast
processes
molecules
with
main
focus
on
photochemistry.
The Journal of Chemical Physics,
Journal Year:
2023,
Volume and Issue:
159(7)
Published: Aug. 18, 2023
Explanation
for
the
modification
of
rates
and
mechanism
reactions
carried
out
in
optical
cavities
still
eludes
us.
Several
studies
indicate
that
cavity-mediated
changes
nature
vibrational
energy
flow
within
a
molecule
may
play
significant
role.
Here,
we
study
model
polaritonic
system,
proposed
analyzed
earlier
by
Fischer
et
al.,
J.
Chem.
Phys.
156,
154305
(2022),
comprising
one-dimensional
isomerization
mode
coupled
to
single
photon
lossless
cavity.
We
show
probability
presence
virtual
photons,
specific
cavity-system
coupling
strengths
cavity
frequencies,
can
exhibit
suppression
or
enhancement
different
choices
initial
reactant
vibropolariton
wavepacket.
observe
qualitative
agreement
between
classical
quantum
average
probabilities
case.
A
part
effects
due
be
rationalized
terms
"chaos-order-chaos"
transition
phase
space
localization
polariton
states
dominantly
participate
dynamics.
On
other
hand,
with
zero
photons
(i.e.,
"dark
cavity"),
is
suppressed
when
frequency
tuned
near
fundamental
reactive
mode.
The
classical-quantum
correspondence
case
unsatisfactory.
In
this
simple
model,
find
arises
interplay
dynamics
tunneling.
We
present
numerically
exact
quantum
dynamics
simulations
using
the
hierarchical
equation
of
motion
(HEOM)
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
(RPV)
mode"
enhances
steady-state
population
excited
states,
leading
an
enhanced
product
at
resonant
condition,
when
frequency
matches
transition
frequency.
Based
on
numerical
observations,
we
analytic
rate
theory
explain
observed
sharp
peak
profile
tuning
match
ground
state
states.
This
further
explains
origin
broadening
profile.
Both
constant
and
simulation
predict
VSC-modified
will
change
quadratically
as
light-matter
strength
increases
this
effect
magnify
lifetime
increases.
To
best
our
knowledge,
is
first
able
behavior
adiabatic
reaction
cavity.
envision
it
offer
invaluable
theoretical
insights
unravel
mysteries
experimentally
coupling-induced
modification.
We
present
numerically
exact
quantum
dynamics
simulations
using
the
hierarchical
equation
of
motion
(HEOM)
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
(RPV)
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
coupling-induced
modifications
We
present
a
theory
that
explains
the
reso-
nance
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)].
Us-
ing
Fermi’s
golden
rule
(FGR),
we
formulate
this
many
molecules
inside
FP
microcavity.
The
clearly
ex-
plains
resonance
condition
observed
VSC
and
provides
theoretical
explanation
why
only
incident
angle
there
effect,
whereas
an
oblique
incidence,
no
apparent
even
though
both
cases
generate
Rabi
splitting
forming
polariton
states.
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
—
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
fuelled
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.
