Simulating the Energy Capture Process in Push–Pull Norbornadiene-Quadricyclane Photoswitches
The Journal of Physical Chemistry Letters,
Год журнала:
2025,
Номер
unknown, С. 4315 - 4325
Опубликована: Апрель 23, 2025
Molecular
switches
based
on
the
norbornadiene-quadricyclane
(NBD-QC)
isomer
pair
are
among
most
promising
candidates
for
applications
in
molecular
solar
thermal
energy
storage
(MOST).
In
these
compounds,
is
captured
through
a
photoinduced
[2
+
2]
cycloaddition
reaction
whose
mechanism
only
partially
understood.
This
holds
true
especially
NBD
derivatives
containing
type
of
push-pull
substitution
pattern
that
was
previously
proven
necessary
to
attain
reasonable
photoisomerization
quantum
yields.
present
contribution,
we
report
computational
investigation
photochemistry
NBD-QC
with
precisely
such
pattern.
Static
calculations
provide
information
structures
excited
electronic
states
involved
reaction,
and
topographies
relevant
ground-
excited-state
potential
surfaces.
Furthermore,
nonadiabatic
dynamics
(NAMD)
simulations
allow
an
estimation
time
scale
yield.
The
simulation
results
paint
detailed
picture
capture
process:
begins
spectroscopically
bright
state
switch.
model
compound
which
performed
NAMD
simulations,
ring
closing
takes
place
roughly
150
fs,
makes
it
one
fastest
known
reactions.
Язык: Английский
DONKEY: A Flexible and Accurate Algorithm for Clustering
Journal of Chemical Theory and Computation,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 2, 2025
We
propose
an
accurate
clustering
algorithm
suitable
for
the
varied
and
multidimensional
data
sets
that
correspond
to
temporal
snapshots
from
on-the-fly
nonadiabatic
trajectory-based
simulations
of
photoexcited
dynamics.
The
approximates
underlying
probability
density
function
using
variable
kernel
estimation,
with
local
maxima
corresponding
cluster
centers.
Each
point
is
then
assigned
one
by
employing
a
maximization
procedure.
Finally,
clusters
artificially
separated
minor
fluctuations
in
are
merged.
does
not
require
parameter
tuning,
which
ensures
flexibility
reduces
risk
bias.
It
tested
on
several
synthetic
sets,
where
it
consistently
outperforms
conventional
algorithms.
As
final
example,
applied
excited
dynamics
norbornadiene
⇌
quadricyclane
(C7H8)
molecular
photoswitch,
demonstrating
how
distinct
reaction
pathways
can
be
identified.
Язык: Английский