Impact of Dipole Self-Energy on Cavity-Induced Nonadiabatic Dynamics
Journal of Chemical Theory and Computation,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 7, 2025
The
coupling
of
matter
to
the
quantized
electromagnetic
field
a
plasmonic
or
optical
cavity
can
be
harnessed
modify
and
control
chemical
physical
properties
molecules.
In
cavities,
term
known
as
dipole
self-energy
(DSE)
appears
in
Hamiltonian
ensure
gauge
invariance.
aim
this
work
is
twofold.
First,
we
introduce
method,
which
has
its
own
merits
complements
existing
methods,
compute
DSE.
Second,
study
impact
DSE
on
cavity-induced
nonadiabatic
dynamics
realistic
system.
For
that
purpose,
various
matrix
elements
are
computed
functions
nuclear
coordinates
system
after
laser
excitation
investigated.
induce
conical
intersections
between
polaritons,
gives
rise
substantial
effects.
shown
slightly
affect
these
light-induced
and,
particular,
break
their
symmetry.
Язык: Английский
Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons
The Journal of Chemical Physics,
Год журнала:
2025,
Номер
162(3)
Опубликована: Янв. 16, 2025
Accurate
rovibrational
molecular
models
are
employed
to
gain
insight
in
high-resolution
into
the
collective
effects
and
intermolecular
processes
arising
when
molecules
gas
phase
interact
with
a
resonant
infrared
(IR)
radiation
mode.
An
efficient
theoretical
approach
is
detailed,
numerical
results
presented
for
HCl,
H2O,
CH4
confined
an
IR
cavity.
It
shown
that
by
employing
rotationally
resolved
model
molecules,
revealing
various
cavity-mediated
interactions
between
field-free
eigenstates,
it
possible
obtain
detailed
understanding
of
physical
governing
energy
level
structure,
absorption
spectra,
dynamic
behavior
systems.
Collective
effects,
due
interaction
identified
shifts,
intensity
borrowing
transfer
occurring
during
Hermitian
or
non-Hermitian
time
propagation.
Язык: Английский
Contributions to the theoretical modeling and understanding of molecular polaritons
Advances in quantum chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Язык: Английский
Selective Excitation of IR-Inactive Modes via Vibrational Polaritons: Insights from Atomistic Simulations
The Journal of Physical Chemistry Letters,
Год журнала:
2025,
Номер
unknown, С. 5034 - 5042
Опубликована: Май 13, 2025
Vibrational
polaritons,
hybrid
light-matter
states
formed
between
molecular
vibrations
and
infrared
(IR)
cavity
modes,
provide
a
novel
approach
for
modifying
chemical
reaction
pathways
energy
transfer
processes.
For
vibrational
polaritons
involving
condensed-phase
molecules,
the
short
polariton
lifetime
raises
debate
over
whether
pumping
may
produce
different
effects
on
molecules
compared
to
directly
exciting
in
free
space
or
under
weak
coupling.
Here,
liquid
methane
strong
coupling,
classical
dynamics
simulations
show
that
upper
(UP)
by
asymmetric
bending
mode
of
can
sometimes
selectively
excite
IR-inactive
symmetric
mode.
This
finding
is
validated
when
system
described
using
both
empirical
force
fields
machine-learning
potentials,
also
qualitative
agreement
with
analytical
theory
rates
based
Fermi's
golden
rule
calculations.
Additionally,
our
study
suggests
polariton-induced
modes
reaches
maximal
efficiency
UP
has
significant
contributions
from
photons
underscoring
importance
hybridization.
As
are
generally
inaccessible
direct
IR
excitation,
highlights
unique
role
formation
controlling
vibrations.
Since
this
process
occurs
after
decays,
it
impact
photochemistry
time
scale
longer
than
lifetime,
as
observed
experiments.
Язык: Английский