Nature Communications,
Journal Year:
2018,
Volume and Issue:
9(1)
Published: Nov. 2, 2018
Abstract
The
formation
of
hybrid
light–molecule
states
(polaritons)
offers
a
new
strategy
to
manipulate
the
photochemistry
molecules.
To
fully
exploit
its
potential,
one
needs
build
toolbox
polaritonic
phenomenologies
that
supplement
those
standard
photochemistry.
By
means
state-of-the-art
computational
approach
extended
strong-coupling
regime,
here
we
disclose
various
mechanisms
peculiar
chemistry:
coherent
population
oscillations
between
polaritons,
quenching
by
trapping
in
dead-end
and
alteration
photochemical
reaction
pathway
quantum
yields.
We
focus
on
azobenzene
photoisomerization,
encompasses
essential
features
complex
reactions
such
as
presence
conical
intersections
coordinates
involving
multiple
internal
modes.
In
strong
coupling
intersection
arises
characterize
role
process.
Our
chemically
detailed
simulations
provide
framework
rationalize
how
impacts
realistic
The Journal of Physical Chemistry Letters,
Journal Year:
2019,
Volume and Issue:
10(18), P. 5519 - 5529
Published: Sept. 1, 2019
We
perform
quantum
dynamics
simulations
to
investigate
new
chemical
reactivities
enabled
by
cavity
electrodynamics.
The
light-matter
interactions
between
the
molecule
and
quantized
radiation
mode
inside
an
optical
create
a
set
of
hybridized
electronic-photonic
states,
so-called
polaritons.
polaritonic
states
adapt
curvatures
from
both
ground
excited
electronic
opening
up
possibilities
control
photochemical
reactions
exploiting
intrinsic
behaviors
interactions.
With
simulations,
we
demonstrate
that
selectivity
model
photoisomerization
reaction
can
be
controlled
tuning
photon
frequency
or
coupling
strength,
providing
ways
manipulate
via
interaction.
further
collective
effects
multiple
molecules.
Our
results
suggest
in
resonance
case,
is
recycled
among
molecules
enable
state
reactions,
thus
effectively
functioning
as
catalyst.
In
nonresonance
emit
absorb
virtual
photons
initiate
through
fundamental
electrodynamics
processes.
These
reveal
basic
principles
polariton
photochemistry
well
promising
take
advantage
photons.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(16), P. 9786 - 9879
Published: Aug. 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.
Annual Review of Physical Chemistry,
Journal Year:
2020,
Volume and Issue:
71(1), P. 435 - 459
Published: March 3, 2020
Bose-Einstein
condensation
describes
the
macroscopic
occupation
of
a
single-particle
mode:
condensate.
This
state
can
in
principle
be
realized
for
any
particles
obeying
statistics;
this
includes
hybrid
light-matter
excitations
known
as
polaritons.
Some
unique
optoelectronic
properties
organic
molecules
make
them
especially
well
suited
realization
polariton
condensates.
Exciton-polaritons
form
optical
cavities
when
electronic
couple
collectively
to
mode
supported
by
cavity.
These
polaritons
obey
bosonic
statistics
at
moderate
densities,
are
stable
room
temperature,
and
have
been
observed
condensed
or
lasing
state.
Understanding
optimal
conditions
requires
careful
modeling
complex
photophysics
molecules.
In
article,
we
introduce
basic
physics
exciton-polaritons
review
experiments
demonstrating
molecular
materials.
ACS Photonics,
Journal Year:
2022,
Volume and Issue:
9(4), P. 1096 - 1107
Published: Feb. 15, 2022
Polaritonic
chemistry
exploits
strong
light-matter
coupling
between
molecules
and
confined
electromagnetic
field
modes
to
enable
new
chemical
reactivities.
In
systems
displaying
this
functionality,
the
choice
of
cavity
determines
both
confinement
number
that
are
involved
in
process.
While
wavelength-scale
optical
cavities
interaction
is
ruled
by
collective
effects,
plasmonic
subwavelength
nanocavities
allow
even
single
reach
coupling.
Due
these
very
distinct
situations,
a
multiscale
theoretical
toolbox
then
required
explore
rich
phenomenology
polaritonic
chemistry.
Within
framework,
each
component
system
(molecules
modes)
needs
be
treated
sufficient
detail
obtain
reliable
results.
Starting
from
general
aspects
light-molecule
interactions
typical
experimental
setups,
we
underline
basic
concepts
should
taken
into
account
when
operating
area
research.
Building
on
considerations,
provide
map
tools
already
available
tackle
applications
molecular
polaritons
at
different
scales.
Throughout
discussion,
draw
attention
successes
challenges
still
ahead
description
ACS Photonics,
Journal Year:
2021,
Volume and Issue:
8(1), P. 85 - 101
Published: Jan. 7, 2021
The
field
of
two-dimensional
(2D)
materials-based
nanophotonics
has
been
growing
at
a
rapid
pace,
triggered
by
the
ability
to
design
nanophotonic
systems
with
in
situ
control,
unprecedented
number
degrees
freedom,
and
build
material
heterostructures
from
bottom
up
atomic
precision.
A
wide
palette
polaritonic
classes
have
identified,
comprising
ultraconfined
optical
fields,
even
approaching
characteristic
length-scales
single
atom.
These
advances
real
boost
for
emerging
quantum
nanophotonics,
where
mechanical
nature
electrons
polaritons
their
interactions
become
relevant.
Examples
include
nonlocal
effects,
ultrastrong
light–matter
interactions,
Cherenkov
radiation,
access
forbidden
transitions,
hydrodynamic
single-plasmon
nonlinearities,
quantization,
topological
so
on.
In
addition
these
intrinsic
phenomena,
2D
can
also
be
used
as
sensitive
probes
properties
that
carries
modes
or
materials
its
vicinity.
Here,
act
probe
otherwise
invisible
excitations,
example,
superconductors,
new
tool
monitor
existence
Berry
curvature
superlattice
effects
twisted
materials.
this
Perspective,
we
present
an
overview
emergent
2D-material
provide
future
perspective
on
prospects
both
fundamental
phenomena
technologies,
such
sensing,
single-photon
sources,
emitters
manipulation.
We
address
four
main
implications:
(i)
featuring
superconductivity
explore
electronic
transport
behaviors,
(ii)
technologies
harnessing
generation,
manipulation,
detection
using
materials,
(iii)
polariton
engineering
enabled
twist
angle
stacking
order
control
van
der
Waals
heterostructures,
(iv)
extreme
light−matter
strong
confinement
light
level
which
tools
manipulate
fields
nanoscale
(e.g.,
chemistry,
high
Purcell
enhancement).
The Journal of Chemical Physics,
Journal Year:
2021,
Volume and Issue:
154(19)
Published: May 18, 2021
One
of
the
most
exciting
and
debated
aspects
polariton
chemistry
is
possibility
that
chemical
reactions
can
be
catalyzed
by
vibrational
strong
coupling
(VSC)
with
confined
optical
modes
in
absence
external
illumination.
Here,
we
report
an
attempt
to
reproduce
enhanced
rate
cyanate
ion
hydrolysis
reported
Hiura
et
al.
[chemRxiv:7234721
(2019)]
when
collective
OH
stretching
vibrations
water
(which
both
solvent
a
reactant)
are
strongly
coupled
Fabry–Pérot
cavity
mode.
Using
piezo-tunable
microcavity,
vacuum
Rabi
splitting
but
fail
observe
any
change
reaction
as
thickness
tuned
out
regime
during
given
experiment.
These
findings
suggest
there
subtleties
involved
successfully
realizing
VSC-catalyzed
kinetics
therefore
motivate
broader
effort
within
community
validate
claims
dark.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(19), P. 11191 - 11229
Published: Sept. 20, 2023
In
this
review,
we
present
the
theoretical
foundations
and
first-principles
frameworks
to
describe
quantum
matter
within
electrodynamics
(QED)
in
low-energy
regime,
with
a
focus
on
polaritonic
chemistry.
By
starting
from
fundamental
physical
mathematical
principles,
first
review
great
detail
ab
initio
nonrelativistic
QED.
The
resulting
Pauli-Fierz
field
theory
serves
as
cornerstone
for
development
of
(in
principle
exact
but
practice)
approximate
computational
methods
such
quantum-electrodynamical
density
functional
theory,
QED
coupled
cluster,
or
cavity
Born–Oppenheimer
molecular
dynamics.
These
treat
light
equal
footing
and,
at
same
time,
have
level
accuracy
reliability
established
chemistry
electronic
structure
theory.
After
an
overview
key
ideas
behind
those
methods,
highlight
their
benefits
understanding
photon-induced
changes
chemical
properties
reactions.
Based
results
obtained
by
identify
open
questions
how
so
far
missing
detailed
can
be
established.
We
finally
give
outlook
future
directions
Physical Review Letters,
Journal Year:
2022,
Volume and Issue:
128(9)
Published: Feb. 28, 2022
Collective
strong
coupling
between
a
disordered
ensemble
of
N
localized
molecular
vibrations
and
resonant
optical
cavity
mode
gives
rise
to
two
polariton
N-1≫2
dark
modes.
Thus,
experimental
changes
in
thermally
activated
reaction
kinetics
due
formation
appear
entropically
unlikely
remain
puzzle.
Here
we
show
that
the
overlooked
modes,
while
parked
at
same
energy
as
bare
vibrations,
are
robustly
delocalized
across
∼2-3
molecules,
yielding
enhanced
channels
vibrational
cooling,
concomitantly
catalyzing
chemical
reaction.
As
an
illustration,
theoretically
≈50%
increase
electron
transfer
rate
product
stabilization.
The
reported
effects
can
arise
when
homogeneous
linewidths
modes
smaller
than
their
spacings.
The Journal of Chemical Physics,
Journal Year:
2023,
Volume and Issue:
158(23)
Published: June 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.