Chemical Reviews,
Год журнала:
2023,
Номер
123(16), С. 9786 - 9879
Опубликована: Авг. 8, 2023
When
molecules
are
coupled
to
an
optical
cavity,
new
light-matter
hybrid
states,
so-called
polaritons,
formed
due
quantum
interactions.
With
the
experimental
demonstrations
of
modifying
chemical
reactivities
by
forming
polaritons
under
strong
interactions,
theorists
have
been
encouraged
develop
methods
simulate
these
systems
and
discover
strategies
tune
control
reactions.
This
review
summarizes
some
exciting
theoretical
advances
in
polariton
chemistry,
ranging
from
fundamental
framework
computational
techniques
applications
spanning
photochemistry
vibrational
coupling.
Even
though
theory
interactions
goes
back
midtwentieth
century,
gaps
knowledge
molecular
electrodynamics
(QED)
only
recently
filled.
We
recent
made
resolving
gauge
ambiguities,
correct
form
different
QED
Hamiltonians
gauges,
their
connections
various
optics
models.
Then,
we
developed
ab
initio
approaches
which
can
accurately
describe
states
a
realistic
molecule-cavity
system.
then
discuss
using
method
advancements.
advancements
where
cavity
is
resonant
electronic
transitions
nonadiabatic
excited
state
dynamics
enable
photochemical
reactivities.
resonance
tuned
vibrations
instead,
ground-state
reaction
modifications
demonstrated
experimentally,
its
mechanistic
principle
remains
unclear.
present
progress
this
mystery.
Finally,
understanding
collective
coupling
regime
between
light
matter,
many
collectively
couple
single
mode
or
modes.
also
lay
out
current
challenges
explain
observed
results.
hope
that
will
serve
as
useful
document
for
anyone
who
wants
become
familiar
with
context
chemistry
thus
significantly
benefit
entire
community.
Chemical Reviews,
Год журнала:
2023,
Номер
123(18), С. 10877 - 10919
Опубликована: Сен. 8, 2023
The
interaction
between
molecular
electronic
transitions
and
electromagnetic
fields
can
be
enlarged
to
the
point
where
distinct
hybrid
light-matter
states,
polaritons,
emerge.
photonic
contribution
these
states
results
in
increased
complexity
as
well
an
opening
modify
photophysics
photochemistry
beyond
what
normally
seen
organic
molecules.
It
is
today
evident
that
polaritons
offer
opportunities
for
photophysics,
which
has
caused
ever-rising
interest
field.
Focusing
on
experimental
landmarks,
this
review
takes
its
reader
from
advent
of
field
polaritonic
chemistry,
over
split
into
polariton
chemistry
photochemistry,
present
day
status
within
photophysics.
To
introduce
field,
starts
with
a
general
description
interactions,
how
enhance
these,
characterizes
coupling
strength.
Then
strongly
coupled
systems
using
Fabry-Perot
plasmonic
cavities
are
described.
This
followed
by
room-temperature
Bose-Einstein
condensation/polariton
lasing
systems.
ends
discussion
benefits,
limitations,
future
developments
strong
exciton-photon
The Journal of Chemical Physics,
Год журнала:
2023,
Номер
158(23)
Опубликована: Июнь 15, 2023
Polariton
chemistry
has
emerged
as
an
appealing
branch
of
synthetic
that
promises
mode
selectivity
and
a
cleaner
approach
to
kinetic
control.
Of
particular
interest
are
the
numerous
experiments
in
which
reactivity
been
modified
by
virtue
performing
reaction
inside
infrared
optical
microcavities
absence
pumping;
this
effort
is
known
"vibropolaritonic
chemistry."
The
optimal
conditions
for
these
observations
(1)
resonance
between
cavity
reactive
modes
at
normal
incidence
(k
=
0)
(2)
monotonic
increase
effect
with
concentration
emitters
sample.
Importantly,
vibropolaritonic
only
experimentally
demonstrated
so-called
"collective"
strong
coupling
regime,
where
there
macroscopic
number
molecules
(rather
than
single
molecule)
coupled
each
photon
microcavity.
Strikingly,
efforts
understand
phenomenon
from
conceptual
standpoint
have
encountered
several
roadblocks,
no
single,
unifying
theory
surfaced
thus
far.
This
Perspective
documents
most
relevant
approaches
taken
theorists,
laying
out
contributions
unresolved
challenges
work.
We
expect
not
serve
primer
experimentalists
theorists
alike
but
also
inform
future
endeavors
quest
ultimate
formalism
chemical
kinetics.
Proceedings of the National Academy of Sciences,
Год журнала:
2023,
Номер
120(15)
Опубликована: Апрель 6, 2023
The
study
of
molecular
polaritons
beyond
simple
quantum
emitter
ensemble
models
(e.g.,
Tavis-Cummings)
is
challenging
due
to
the
large
dimensionality
these
systems
and
complex
interplay
electronic
nuclear
degrees
freedom.
This
complexity
constrains
existing
either
coarse-grain
rich
physics
chemistry
freedom
or
artificially
limit
description
a
small
number
molecules.
In
this
work,
we
exploit
permutational
symmetries
drastically
reduce
computational
cost
ab
initio
dynamics
simulations
for
N.
Furthermore,
discover
an
emergent
hierarchy
timescales
present
in
systems,
that
justifies
use
effective
single
molecule
approximately
capture
entire
ensemble,
approximation
becomes
exact
as
N
→
∞.
We
also
systematically
derive
finite
corrections
show
addition
k
extra
molecules
enough
account
phenomena
whose
rates
scale
풪(N-k).
Based
on
result,
discuss
how
seamlessly
modify
single-molecule
strong
coupling
describe
corresponding
ensemble.
call
approach
collective
using
truncated
equations
(CUT-E),
benchmark
it
against
well-known
results
polariton
relaxation
rates,
apply
universal
cavity-assisted
energy
funneling
mechanism
between
different
species.
Beyond
being
computationally
efficient
tool,
formalism
provides
intuitive
picture
understanding
role
bright
dark
states
chemical
reactivity,
necessary
generate
robust
strategies
chemistry.
Chemical Reviews,
Год журнала:
2023,
Номер
123(13), С. 8099 - 8126
Опубликована: Июнь 30, 2023
The
coherent
exchange
of
energy
between
materials
and
optical
fields
leads
to
strong
light-matter
interactions
so-called
polaritonic
states
with
intriguing
properties,
halfway
light
matter.
Two
decades
ago,
research
on
these
interactions,
using
cavity
(vacuum)
fields,
remained
for
the
most
part
province
physicist,
a
focus
inorganic
requiring
cryogenic
temperatures
carefully
fabricated,
high-quality
cavities
their
study.
This
review
explores
history
recent
acceleration
interest
in
application
molecular
properties
processes.
enormous
collective
oscillator
strength
dense
films
organic
molecules,
aggregates,
allows
vacuum
field
coupling
be
achieved
at
room
temperature,
even
rapidly
highly
lossy
metallic
cavities.
has
put
associated
phenomena
fingertips
laboratory
chemists,
scientists,
biochemists
as
potentially
new
tool
control
chemistry.
exciting
that
have
emerged
suggest
are
genuine
relevance
within
material
landscape.
Applied Physics Reviews,
Год журнала:
2023,
Номер
10(2)
Опубликована: Июнь 1, 2023
In
the
past
20
years,
we
have
reached
a
broad
understanding
of
many
light-driven
phenomena
in
nanoscale
systems.
The
temporal
dynamics
excited
states
are
instead
quite
challenging
to
explore,
and,
at
same
time,
crucial
study
for
origin
fundamental
physical
and
chemical
processes.
this
review,
examine
current
state
prospects
ultrafast
driven
by
plasmons
both
from
applied
point
view.
This
research
area
is
referred
as
plasmonics
represents
an
outstanding
playground
tailor
control
fast
optical
electronic
processes
nanoscale,
such
switching,
single
photon
emission,
strong
coupling
interactions
photochemical
reactions.
Here,
provide
overview
field
describe
methodologies
monitor
with
timescales
terms
modeling
experimental
characterization.
Various
directions
showcased,
among
others
recent
advances
plasmon-driven
chemistry
multi-functional
plasmonics,
which
charge,
spin,
lattice
degrees
freedom
exploited
active
properties
materials.
As
focus
shifts
development
practical
devices,
all-optical
transistors,
also
emphasize
new
materials
applications
highlight
relativistic
realm.
latter
promising
potential
fusion
or
particle
light
sources
providing
attosecond
duration.
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.
Chemical Reviews,
Год журнала:
2024,
Номер
124(5), С. 2512 - 2552
Опубликована: Фев. 28, 2024
Molecular
polaritons
are
quasiparticles
resulting
from
the
hybridization
between
molecular
and
photonic
modes.
These
composite
entities,
bearing
characteristics
inherited
both
constituents,
exhibit
modified
energy
levels
wave
functions,
thereby
capturing
attention
of
chemists
in
past
decade.
The
potential
to
modify
chemical
reactions
has
spurred
many
investigations,
alongside
efforts
enhance
manipulate
optical
responses
for
quantum
applications.
This
Review
centers
on
experimental
advances
this
burgeoning
field.
Commencing
with
an
introduction
fundamentals,
including
theoretical
foundations
various
cavity
architectures,
we
discuss
outcomes
polariton-modified
reactions.
Furthermore,
navigate
through
ongoing
debates
uncertainties
surrounding
underpinning
mechanism
innovative
method
controlling
chemistry.
Emphasis
is
placed
gaining
a
comprehensive
understanding
dynamics
polaritons,
particular,
vibrational
polaritons─a
pivotal
facet
steering
Additionally,
unique
capability
coherent
two-dimensional
spectroscopy
dissect
polariton
dark
mode
dynamics,
offering
insights
into
critical
components
within
that
alter
We
further
expand
utility
applications
as
well
precise
manipulation
polarizations,
notably
context
chiral
phenomena.
discussion
aspires
ignite
deeper
curiosity
engagement
revealing
physics
properties,
broad
fascination
harnessing
environments
control
Journal of Chemical Theory and Computation,
Год журнала:
2024,
Номер
20(3), С. 1214 - 1227
Опубликована: Янв. 30, 2024
Polariton
chemistry
has
attracted
great
attention
as
a
potential
route
to
modify
chemical
structure,
properties,
and
reactivity
through
strong
interactions
among
molecular
electronic,
vibrational,
or
rovibrational
degrees
of
freedom.
A
rigorous
theoretical
treatment
polaritons
requires
the
matter
photon
freedom
on
equal
quantum
mechanical
footing.
In
limit
electronic
ultrastrong
coupling
one
few
molecules,
it
is
desirable
treat
using
tools
ab
initio
chemistry,
yielding
an
approach
we
refer
cavity
electrodynamics,
where
are
treated
at
level
electrodynamics.
Here,
present
called
Cavity
Quantum
Electrodynamics
Complete
Active
Space
Configuration
Interaction
theory
provide
ground-
excited-state
polaritonic
surfaces
with
balanced
description
correlation
effects
photonic
This
method
provides
platform
for
electrodynamics
when
both
electron
light–matter
important
step
toward
computational
approaches
that
yield
multiple
energy
couplings
can
be
leveraged
dynamics
simulations
polariton
chemistry.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(23)
Опубликована: Апрель 8, 2024
Abstract
Polaritonic
chemistry
is
emerging
as
a
powerful
approach
to
modifying
the
properties
and
reactivity
of
molecules
materials.
However,
probing
how
electronics
dynamics
molecular
systems
change
under
strong
coupling
has
been
challenging
due
narrow
range
spectroscopic
techniques
that
can
be
applied
in
situ.
Here
we
develop
microfluidic
optical
cavities
for
vibrational
(VSC)
are
compatible
with
nuclear
magnetic
resonance
(NMR)
spectroscopy
using
standard
liquid
NMR
tubes.
VSC
shown
influence
equilibrium
between
two
conformations
balance
sensitive
London
dispersion
forces,
revealing
an
apparent
constant
VSC.
In
all
compounds
studied,
does
not
induce
detectable
changes
chemical
shifts,
J‐couplings,
or
spin‐lattice
relaxation
times.
This
unexpected
finding
indicates
substantially
affect
electron
density
distributions,
turn
profound
implications
possible
mechanisms
at
play
polaritonic
suggests
emergence
collective
behavior
critical.