Nanophotonics,
Год журнала:
2024,
Номер
13(14), С. 2575 - 2590
Опубликована: Апрель 16, 2024
Abstract
The
emerging
field
of
molecular
cavity
polaritons
has
stimulated
a
surge
experimental
and
theoretical
activities
presents
unique
opportunity
to
develop
the
many-body
simulation
methodology.
This
paper
numerical
scheme
for
extraction
key
kinetic
information
lossy
based
on
transfer
tensor
method
(TTM).
Steady
state,
relaxation
timescales,
oscillatory
phenomena
can
all
be
deduced
directly
from
set
tensors
without
need
long-time
simulation.
Moreover,
we
generalize
TTM
disordered
systems
by
sampling
dynamical
maps
achieve
fast
convergence
disordered-averaged
dynamics
using
small
realizations.
Together,
these
techniques
provide
toolbox
characterizing
interplay
loss,
disorder,
cooperativity
in
polariton
allow
us
predict
unusual
dependences
initial
excitation
photon
decay
rate,
strength
type
models.
Thus,
example
polaritons,
have
demonstrated
significant
potential
use
toward
both
efficient
computation
crucial
about
short-time
trajectories.
The Journal of Physical Chemistry Letters,
Год журнала:
2024,
Номер
15(19), С. 5208 - 5214
Опубликована: Май 8, 2024
We
demonstrate
that
collective
vibrational
strong
coupling
of
molecules
in
thermal
equilibrium
can
give
rise
to
significant
local
electronic
polarizations
the
thermodynamic
limit.
do
so
by
first
showing
full
nonrelativistic
Pauli–Fierz
problem
an
ensemble
strongly
coupled
dilute-gas
limit
reduces
cavity
Born–Oppenheimer
approximation
a
cavity–Hartree
equation
for
structure.
Consequently,
each
individual
molecule
experiences
self-consistent
dipoles
all
other
molecules,
which
amount
non-negligible
values
(large
ensembles).
Thus,
alter
localized
"hotspots"
within
ensemble.
Moreover,
discovered
cavity-induced
polarization
pattern
possesses
zero
net
polarization,
resembles
continuous
form
spin
glass
(or
better
glass).
Our
findings
suggest
thorough
understanding
polaritonic
chemistry,
requires
treatment
dressed
structure,
numerous,
far
overlooked,
physical
mechanisms.
Physical Review Research,
Год журнала:
2025,
Номер
7(1)
Опубликована: Март 5, 2025
Despite
recent
numerical
evidence,
one
of
the
fundamental
theoretical
mysteries
polaritonic
chemistry
is
how
and
if
collective
strong
coupling
can
induce
local
changes
electronic
structure
to
modify
chemical
properties.
Here
we
present
nonperturbative
analytic
results
for
a
model
system
consisting
an
ensemble
N
harmonic
molecules
under
vibrational
(VSC)
that
alters
our
understanding
this
question.
By
applying
cavity
Born-Oppenheimer
partitioning
on
Pauli-Fierz
Hamiltonian
in
dipole
approximation,
dressed
many-molecule
problem
be
solved
nonperturbatively
analytically
dilute
limit,
i.e.,
self-consistent
solution
with
mean-field
Hartree-product
wave
function
becomes
exact.
We
discover
molecular
polarizabilities
are
modified
even
case
vanishingly
small
single-molecule
couplings.
Consequently,
polarization
mechanism
persists
large-N
limit.
In
contrast,
perturbative
calculation
based
uncoupled
leads
qualitatively
erroneous
scaling
behavior
vanishing
effects
large-N
Nevertheless,
exact
(self-consistent)
determined
from
simulations
instead.
Our
observations
demonstrate
hitherto
existing
collective-scaling
arguments
insufficient
they
pave
way
refined
single-
(or
few-)molecule
strong-coupling
systems
coupling.
Published
by
American
Physical
Society
2025
The Journal of Physical Chemistry Letters,
Год журнала:
2023,
Номер
14(36), С. 8024 - 8033
Опубликована: Авг. 31, 2023
Experimental
studies
indicate
that
optical
cavities
can
affect
chemical
reactions
through
either
vibrational
or
electronic
strong
coupling
and
the
quantized
cavity
modes.
However,
current
understanding
of
interplay
between
molecules
confined
light
modes
is
incomplete.
Accurate
theoretical
models
take
into
account
intermolecular
interactions
to
describe
ensembles
are
therefore
essential
understand
mechanisms
governing
polaritonic
chemistry.
We
present
an
ab
initio
Hartree-Fock
ansatz
in
framework
Born-Oppenheimer
approximation
study
strongly
interacting
with
cavity.
This
provides
a
nonperturbative,
self-consistent
description
coupled
molecular
ensembles,
taking
cavity-mediated
dipole
self-energy
contributions.
To
demonstrate
capability
ansatz,
we
collective
effects
diatomic
hydrogen
fluoride
molecules.
Our
results
highlight
importance
dipole-dipole
interactions,
which
lead
energetic
changes
individual
ensemble.
The Journal of Physical Chemistry Letters,
Год журнала:
2023,
Номер
14(36), С. 8261 - 8267
Опубликована: Сен. 7, 2023
Recent
experiments
in
polariton
chemistry
have
demonstrated
that
reaction
rates
can
be
modified
by
vibrational
strong
coupling
to
an
optical
cavity
mode.
Importantly,
this
modification
occurs
only
when
the
frequency
of
mode
is
tuned
closely
match
a
molecular
frequency.
This
sharp
resonance
behavior
has
proved
difficult
capture
theoretically.
Only
recently
did
Lindoy
et
al.
[
Chemical Physics Reviews,
Год журнала:
2023,
Номер
4(4)
Опубликована: Ноя. 13, 2023
Organic
polaritonics
has
emerged
as
a
captivating
interdisciplinary
field
that
marries
the
complexities
of
organic
photophysics
with
fundamental
principles
quantum
optics.
By
harnessing
strong
light–matter
coupling
in
materials,
exciton–polaritons
offer
unique
opportunities
for
advanced
device
performance,
including
enhanced
energy
transport
and
low-threshold
lasing,
well
new
functionalities
like
polariton
chemistry.
In
this
review,
we
delve
into
foundational
from
an
experimental
perspective,
highlighting
key
states,
processes,
timescales
govern
phenomena.
Our
review
centers
on
spectroscopy
exciton–polaritons.
We
overview
primary
spectroscopic
approaches
reveal
phenomena,
discuss
challenges
disentangling
polaritonic
signatures
spectral
artifacts.
how
due
to
their
complex
disordered
nature,
not
only
present
conventional
models
but
also
provide
physics,
manipulating
dark
electronic
states.
As
research
continues
grow,
increasingly
materials
devices,
serves
valuable
introductory
guide
researchers
navigating
intricate
landscape
polaritonics.
The Journal of Chemical Physics,
Год журнала:
2023,
Номер
159(8)
Опубликована: Авг. 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
Physical Review Research,
Год журнала:
2024,
Номер
6(1)
Опубликована: Фев. 29, 2024
We
present
a
powerful
formalism,
disordered
collective
dynamics
using
truncated
equations
(d-CUT-E),
to
simulate
the
ultrafast
quantum
of
molecular
polaritons
in
strong
coupling
regime,
where
ensemble
N≫106
molecules
couples
cavity
mode.
Notably,
we
can
capture
this
with
hosting
single
molecule
∼Nbins
electronic
states,
Nbins≪N
is
number
bins
discretizing
disorder
distribution.
Using
d-CUT-E
conclude
that
coupling,
as
evaluated
from
linear
optical
spectra,
be
poor
proxy
for
polariton
chemistry.
For
highly
ensembles,
total
reaction
yield
upon
broadband
excitation
identical
outside
cavity,
while
narrowband
produces
distinct
yields
solely
due
differences
initial
states
prepared
prior
reaction.
Published
by
American
Physical
Society
2024
The Journal of Chemical Physics,
Год журнала:
2024,
Номер
160(18)
Опубликована: Май 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,
Год журнала:
2024,
Номер
13(14), С. 2601 - 2615
Опубликована: Фев. 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.