The Journal of Physical Chemistry Letters,
Год журнала:
2024,
Номер
15(32), С. 8211 - 8217
Опубликована: Авг. 5, 2024
We
leveraged
strong
light–matter
coupling,
a
quantum
process
generating
hybridized
states,
to
prepare
phototransistors
using
donor–acceptor
pairs
that
transfer
energy
via
Rabi
oscillations.
In
prototype
experiment,
we
used
cyanine
J-aggregate
(TDBC;
donor)
and
MoS2
monolayer
(acceptor)
in
field
effect
transistor
cavity
study
photoresponsivity.
Energy
migrates
through
the
newly
formed
polaritonic
ladder,
with
enhanced
device
efficiency
when
is
resonant
donors.
A
theoretical
model
based
on
time-dependent
Schrödinger
equation
helped
interpret
results,
states
acting
as
funnel
monolayer.
These
findings
suggest
novel
applications
of
coupling
materials.
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Polaritons
lose
delocalization
in
energetically
disordered
systems.
A
large
Rabi
splitting
about
3–4
times
of
the
inhomogeneous
linewidths
is
required
to
restore
delocalization.
This
study
can
guide
future
rational
experiment
designs.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Авг. 4, 2024
Strong
coupling
between
molecules
and
confined
light
modes
of
optical
cavities
to
form
polaritons
can
alter
photochemistry,
but
the
origin
this
effect
remains
largely
unknown.
While
theoretical
models
suggest
a
suppression
photochemistry
due
formation
new
polaritonic
potential
energy
surfaces,
many
these
do
not
account
for
energetic
disorder
among
molecules,
which
is
unavoidable
at
ambient
conditions.
Here,
we
combine
simulations
experiments
show
that
an
ultra-fast
photochemical
reaction
such
thermal
prevents
modification
surface
radiative
decay
lossy
cavity
modes.
We
also
excitation
spectrum
under
strong
product
bare
absorption
molecule-cavity
system,
suggesting
act
as
gateways
channeling
into
molecule,
then
reacts
normally.
Our
results
therefore
imply
provides
means
tune
action
rather
than
change
reaction.
The
aim
chemistry
control
reactions
by
placing
inside
cavities.
authors
directly
possible
disorder,
in
real
experiments,
mostly
channel
molecular
excitations.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Photochemical
reactions
enable
the
synthesis
of
energetically
unfavorable
compounds
but
often
require
irradiation
with
ultraviolet
light,
which
potentially
induces
side
reactions.
Experiments
show
that
light-matter
strong
coupling
affects
chemical
properties,
though
the
underlying
mechanism
remains
unclear.
A
major
challenge
is
to
perform
reliable
and
affordable
simulation
of
molecular
behavior
when
many
molecules
are
collectively
coupled
same
optical
mode.
This
paper
presents
an
quantum
electrodynamics
cluster
method
for
collective
regime.
The
model
describes
electronic
electron-photon
correlation
within
a
subsystem,
while
simplified
description
polaritonic
excitations
allows
realistic
microscopic
coupling.
developed
framework
provides
computationally
tractable
route
accurately
simulate
molecule
in
environment,
which
unfeasible
several
treated
explicitly.
We
investigate
properties
argon
dimer
under
In
single-molecule
regime
(large
coupling),
potential
energies
substantially
modified,
weakening
excimer
bond.
contrast,
(small
coupling,
large
number
molecules),
ground
state
energy
surface
first
vibrational
levels
excited
do
not
change
significantly.
However,
produces
abrupt
transition
landscape
excimer,
causing
higher
behave
similarly
vibrations
state.
expect
formation
be
inhibited
by
conclude
altered
via
distinct
mechanisms
regimes.
also
discuss
fundamental
aspects
chemistry,
such
as
resonance
conditions
sudden
changes
critical
strength
achieved.
Published
American
Physical
Society
2025
The Journal of Chemical Physics,
Год журнала:
2025,
Номер
162(1)
Опубликована: Янв. 2, 2025
In
this
work,
we
investigate
anharmonic
vibrational
polaritons
formed
due
to
strong
light–matter
interactions
in
an
optical
cavity
between
radiation
modes
and
vibrations
beyond
the
long-wavelength
limit.
We
introduce
a
conceptually
simple
description
of
interactions,
where
spatially
localized
couple
vibrations.
Within
theoretical
framework,
employ
self-consistent
phonon
theory
dynamical
mean-field
efficiently
simulate
momentum-resolved
vibrational-polariton
spectra,
including
effects
anharmonicity.
Numerical
simulations
model
systems
demonstrate
accuracy
applicability
our
approach.
The Journal of Chemical Physics,
Год журнала:
2024,
Номер
161(7)
Опубликована: Авг. 15, 2024
Gas-phase
molecules
are
a
promising
platform
to
elucidate
the
mechanisms
of
action
and
scope
polaritons
for
optical
control
chemistry.
Polaritons
arise
from
strong
coupling
dipole-allowed
molecular
transition
with
photonic
mode
an
cavity.
There
is
mounting
evidence
modified
reactivity
under
polaritonic
conditions;
however,
complex
condensed-phase
environment
most
experimental
demonstrations
impedes
mechanistic
understanding
this
phenomenon.
While
gas
phase
was
playground
early
efforts
in
atomic
cavity
quantum
electrodynamics,
we
have
only
recently
demonstrated
formation
these
conditions.
Studying
isolated
gas-phase
would
eliminate
solvent
interactions
enable
state
resolution
reaction
progress.
In
Perspective,
contextualize
recent
field
polariton
chemistry
offer
practical
guide
design
moving
forward.
Abstract
Polaritons
are
quantum
mechanical
superpositions
of
photon
states
with
elementary
excitations
in
molecules
and
solids.
The
light–matter
admixture
causes
a
characteristic
frequency-momentum
dispersion
shared
by
all
polaritons
irrespective
the
microscopic
nature
material
that
could
entail
charge,
spin,
lattice
or
orbital
effects.
retain
strong
nonlinearities
their
matter
component
simultaneously
inherit
ray-like
propagation
light.
prompt
new
properties,
enable
opportunities
for
spectroscopy/imaging,
empower
simulations
give
rise
to
forms
synthetic
matter.
Here,
we
review
emergent
effects
rooted
polaritonic
quasiparticles
wide
variety
physical
implementations.
We
present
broad
portfolio
platforms
phenomena
what
term
discuss
unifying
aspects
across
different
implementations
focus
on
recent
developments
in:
imaging,
cavity
electrodynamics
materials
engineering,
topology
nonlinearities,
as
well
polaritonics.
The Journal of Physical Chemistry A,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 9, 2025
The
development
of
reliable
ab
initio
methods
for
light-matter
strong
coupling
is
necessary
a
deeper
understanding
molecular
polaritons.
recently
developed
quantum
electrodynamics
Hartree-Fock
model
(SC-QED-HF)
provides
cavity-consistent
orbitals,
overcoming
several
difficulties
related
to
the
simpler
QED-HF
wave
function.
In
this
paper,
we
further
develop
method
by
implementing
response
theory
SC-QED-HF.
We
compare
derived
linear
equations
with
time-dependent
and
discuss
validity
equivalence
relations
connecting
matter
electromagnetic
observables.
Our
results
show
that
electron-photon
correlation
induces
an
excitation
redshift
compared
energies,
effect
dipole
self-energy
on
ground
excited
state
properties
different
basis
sets.
The Journal of Chemical Physics,
Год журнала:
2024,
Номер
161(10)
Опубликована: Сен. 9, 2024
Strong
light–matter
coupling
within
an
optical
cavity
leverages
the
collective
interactions
of
molecules
and
confined
electromagnetic
fields,
giving
rise
to
possibilities
modifying
chemical
reactivity
molecular
properties.
While
responses,
such
as
enhanced
Rabi
splitting,
are
often
observed,
overall
effect
on
systems
remains
ambiguous
for
a
large
number
molecules.
In
this
paper,
we
investigate
non-adiabatic
electron
transfer
process
in
donor–acceptor
pairs
influenced
by
excitation
local
dynamics.
Using
timescale
difference
between
reorganization
thermal
fluctuations,
derive
analytical
formulas
rate
constant
polariton
relaxation
rate.
These
apply
any
(N)
account
induced
photon
coupling.
Our
findings
reveal
non-monotonic
dependence
N,
which
can
be
understood
interplay
relaxation.
As
result,
cavity-induced
quantum
yield
increases
linearly
with
N
small
(as
predicted
simple
Dicke
model)
but
shows
turnover
suppression
N.
We
also
interrelate
bath
frequency
molecules,
suggesting
optimal
maximizing
enhancement.
The
analysis
provides
insight
understanding
light
transfer,
helping
predict
condition
effective
cavity-controlled
reactivity.