Abstract
Optical
antenna
resonators
enable
control
of
light‐matter
interactions
on
the
nano‐scale
via
electron–photon
hybrid
states
in
strong
coupling.
Specifically,
mid‐infrared
(MIR)
nano‐antennas
coupled
to
saturable
intersubband
transitions
multi‐quantum‐well
(MQW)
semiconductor
heterostructures
allow
for
coupling
strength
be
tuned
through
resonance
and
field
intensity.
Here,
tip‐enhanced
variation
antenna‐MQW
across
is
demonstrated,
with
a
spatially‐dependent
varying
from
73
(strong
coupling)
24
(weak
coupling).
This
behavior
modeled
based
spatially
dependent
local
constructive
destructive
interference
between
tip
fields.
Using
quantum‐mechanical
density‐matrix
model
MQW
system
its
designed
values
transition
dipole
moment,
doping
density,
population
decay
time,
picosecond
IR
pulse
associated
induced
strong‐field
saturation
effects
are
described.
These
results
present
new
regime
nonlinear
dynamic
manipulation
quantum
nanoscale
infrared,
perspective
regarding
extension
molecular
vibrations.
Journal of Chemical Theory and Computation,
Journal Year:
2023,
Volume and Issue:
19(24), P. 9278 - 9289
Published: Dec. 12, 2023
Recent
experiments
have
revealed
the
profound
effect
of
strong
light-matter
interactions
in
optical
cavities
on
electronic
ground
state
molecular
systems.
This
phenomenon,
known
as
vibrational
coupling,
can
modify
reaction
rates
and
induce
formation
polaritons,
hybrid
states
involving
both
photon
modes,
modes
molecules.
We
present
an
ab
initio
methodology
based
cavity
Born-Oppenheimer
Hartree-Fock
ansatz,
which
is
specifically
powerful
for
ensembles
molecules,
to
calculate
vibro-polaritonic
IR
spectra.
method
allows
a
comprehensive
analysis
these
states.
Our
semiclassical
approach,
validated
against
full
quantum
simulations,
reproduces
key
features
The
underlying
analytic
gradients
also
allow
optimization
cavity-coupled
systems
performing
dynamics
simulations.
Communications Materials,
Journal Year:
2024,
Volume and Issue:
5(1)
Published: June 28, 2024
Abstract
Recent
experiments
demonstrate
polaritons
under
the
vibrational
strong
coupling
(VSC)
regime
can
modify
chemical
reactivity.
Here,
we
present
a
complete
theory
of
VSC-modified
rate
constants
when
single
molecule
to
an
optical
cavity,
where
role
photonic
mode
lifetime
is
understood.
The
analytic
expression
exhibits
sharp
resonance
behavior,
maximum
constant
reached
cavity
frequency
matches
vibration
frequency.
explains
why
VSC
modification
closely
resembles
spectra
outside
cavity.
Further,
discussed
temperature
dependence
constants.
agrees
well
with
numerically
exact
hierarchical
equations
motion
(HEOM)
simulations
for
all
explored
regimes.
Finally,
condition
at
normal
incidence
considering
in-plane
momentum
inside
Fabry-Pérot
Physical review. A/Physical review, A,
Journal Year:
2024,
Volume and Issue:
109(5)
Published: May 23, 2024
Quantum-electrodynamical
density-functional
theory
(QEDFT)
provides
a
promising
avenue
for
exploring
complex
light-matter
interactions
in
optical
cavities
real
materials.
Similar
to
conventional
theory,
the
Kohn-Sham
formulation
of
QEDFT
needs
approximations
generally
unknown
exchange-correlation
functional.
In
addition
usual
electron-electron
potential,
an
approximation
electron-photon
potential
is
needed.
A
recent
exchange
functional
[C.
Schäfer
,
],
derived
from
equation
motion
nonrelativistic
Pauli-Fierz
Hamiltonian,
shows
robust
performance
one-dimensional
systems
across
weak-
and
strong-coupling
regimes.
Yet,
its
reproducing
electron
densities
higher
dimensions
remains
unexplored.
Here
we
consider
this
one-
three-dimensional
finite
weak
strong
couplings.
The
excellent
results
ultrastrong-coupling
regime.
However,
ensure
accuracy
also
weak-coupling
regime
dimensions,
introduce
computationally
efficient
renormalization
factor
functional,
which
accounts
part
correlation
contribution.
These
findings
extend
applicability
photon-exchange-based
functionals
realistic
cavity-matter
systems,
fostering
field
cavity
QED
(quantum-electrodynamics)
materials
engineering.
Published
by
American
Physical
Society
2024
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(48)
Published: Aug. 19, 2024
Abstract
Vibrational
strong
coupling
can
modify
chemical
reaction
pathways
in
unconventional
ways.
Thus
far,
Fabry‐Perot
cavities
formed
by
pairs
of
facing
mirrors
have
been
mostly
utilized
to
achieve
vibrational
coupling.
In
this
study,
we
demonstrate
the
application
non‐local
metasurfaces
that
sustain
surface
lattice
resonances,
enabling
reactions
under
We
show
solvolysis
kinetics
para
‐nitrophenyl
acetate
be
accelerated
a
factor
2.7
carbonyl
bond
solvent
and
solute
with
resonance.
Our
work
introduces
new
platform
investigate
polaritonic
reactions.
contrast
cavities,
define
open
optical
single
surfaces,
which
removes
alignment
hurdles,
facilitating
chemistry
across
large
areas.
Abstract
Optical
antenna
resonators
enable
control
of
light‐matter
interactions
on
the
nano‐scale
via
electron–photon
hybrid
states
in
strong
coupling.
Specifically,
mid‐infrared
(MIR)
nano‐antennas
coupled
to
saturable
intersubband
transitions
multi‐quantum‐well
(MQW)
semiconductor
heterostructures
allow
for
coupling
strength
be
tuned
through
resonance
and
field
intensity.
Here,
tip‐enhanced
variation
antenna‐MQW
across
is
demonstrated,
with
a
spatially‐dependent
varying
from
73
(strong
coupling)
24
(weak
coupling).
This
behavior
modeled
based
spatially
dependent
local
constructive
destructive
interference
between
tip
fields.
Using
quantum‐mechanical
density‐matrix
model
MQW
system
its
designed
values
transition
dipole
moment,
doping
density,
population
decay
time,
picosecond
IR
pulse
associated
induced
strong‐field
saturation
effects
are
described.
These
results
present
new
regime
nonlinear
dynamic
manipulation
quantum
nanoscale
infrared,
perspective
regarding
extension
molecular
vibrations.
