Realistic Ab Initio Predictions of Excimer Behavior under Collective Light-Matter Strong Coupling
Physical Review X,
Journal Year:
2025,
Volume and Issue:
15(2)
Published: May 5, 2025
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
Language: Английский
Strong Coupling Quantum Electrodynamics Hartree–Fock Response Theory
The Journal of Physical Chemistry A,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 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.
Language: Английский
Molecular Polarizability under Vibrational Strong Coupling
Journal of Chemical Theory and Computation,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 14, 2025
Polaritonic
chemistry
offers
the
possibility
of
modifying
molecular
properties
and
even
influencing
chemical
reactivity
through
strong
coupling
between
vibrational
transitions
confined
light
modes
in
optical
cavities.
Despite
considerable
theoretical
progress,
due
to
complexity
coupled
light-matter
system,
fundamental
mechanism
how
if
collective
can
induce
local
changes
individual
molecules
is
still
unclear.
We
derive
an
analytical
formulation
static
polarizabilities
within
linear-response
theory
for
under
using
cavity
Born-Oppenheimer
Hartree-Fock
ansatz.
This
ab-initio
method
consistently
describes
electron-photon
interactions
ensembles
molecules.
For
different
types
ensembles,
we
observed
dipole
moments
that
are
induced
by
coupling.
Furthermore,
used
calculate
vibro-polaritonic
Raman
spectra
harmonic
approximation.
allows
us
comprehensively
compare
effect
on
IR
equal
footing.
Language: Английский