Improving the Reliability of, and Confidence in, DFT Functional Benchmarking through Active Learning
Journal of Chemical Theory and Computation,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 2, 2025
Validating
the
performance
of
exchange-correlation
functionals
is
vital
to
ensure
reliability
density
functional
theory
(DFT)
calculations.
Typically,
these
validations
involve
benchmarking
data
sets.
Currently,
such
sets
are
usually
assembled
in
an
unprincipled
manner,
suffering
from
uncontrolled
chemical
bias,
and
limiting
transferability
results
a
broader
space.
In
this
work,
data-efficient
solution
based
on
active
learning
explored
address
issue.
Focusing─as
proof
principle─on
pericyclic
reactions,
we
start
BH9
set
design
reaction
space
around
initial
by
combinatorially
combining
templates
substituents.
Next,
surrogate
model
trained
predict
standard
deviation
activation
energies
computed
across
selection
20
distinct
DFT
functionals.
With
model,
designed
explored,
enabling
identification
challenging
regions,
i.e.,
regions
with
large
divergence,
for
which
representative
reactions
subsequently
acquired
as
additional
training
points.
Remarkably,
it
turns
out
that
function
mapping
molecular
structure
divergence
readily
learnable;
convergence
reached
upon
acquisition
fewer
than
100
reactions.
our
final
updated
more
challenging─and
arguably
representative─pericyclic
curated,
demonstrate
has
changed
significantly
compared
original
subset.
Язык: Английский
Exploring Forsterite Surface Catalysis in HCN Polymerization: Computational Insights for Astrobiology and Prebiotic Chemistry
ACS Earth and Space Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 17, 2025
Understanding
the
catalytic
role
of
cosmic
mineral
surfaces
is
crucial
for
elucidating
chemical
evolution
needed
emergence
life
on
Earth
and
other
planetary
systems.
In
this
study,
silicate
forsterite
(Mg2SiO4)
in
synthesis
iminoacetonitrile
(IAN,
HN=CH-CN)
from
condensation
two
hydrogen
cyanide
(HCN)
molecules
investigated
through
quantum
mechanical
simulations.
Using
density
functional
theory
calculations,
potential
energy
alongside
kinetics
various
surface-mediated
reactions
leading
to
formation
IAN
are
characterized.
The
effectiveness
as
a
catalyst
delicate
balance
surface
reactivity:
one
side,
deprotonation
HCN
mandatory
trigger
dimerization;
species
should
be
weakly
bound
surface,
thus
allowing
their
diffusion
meet
with
each
other.
work
reveals
interesting
counterintuitive
results:
(120)
(101)
(the
less
reactive
ones)
exhibit
favorable
properties
reaction,
detriment
(111)
(one
most
reactive).
implications
these
findings
astrobiology
prebiotic
chemistry
fields
laboratory
experiments
discussed,
highlighting
silicates
complex
organic
molecules.
Язык: Английский
Toward Establishing the Principles of Electronic Structure Modeling of Battery Interfaces
The Journal of Physical Chemistry C,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 17, 2025
Язык: Английский
Symmetric and Unsymmetric Bifurcating Surfaces of Ambimodal Reactions: Origin of Electronic Behavior in Post-Transition State Bifurcation
Rama Krishna Kadiyam,
Akanksha Ashok Sangolkar,
Ravinder Pawar
и другие.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Июнь 2, 2025
Ambimodal
reactions
are
distinctive
in
their
ability
to
produce
multiple
products
from
a
single
transition
state
(TS)
through
bifurcation
of
the
potential
energy
surface
(PES),
mechanism
which
is
inadequately
described
by
conventional
kinetic
theory.
This
report
gains
crucial
insight
into
electronic
structure
and
behavior
underlying
dimerization
azacyclopentadienone
resolve
ambiguity
complex
mechanisms.
The
result
rationalizes
critical
interplay
electrons
on
PES
that
governs
nature
duration
reaction.
Reactions
symmetric
surfaces
have
high
degree
asynchronicity
proportional
bidirectional
electron
delocalization,
leading
longer
reaction
durations.
reactant
major
product
unsymmetric
streamlined
independent
competing
trajectories,
flow
synchronous.
outcomes
provide
proof
concept
minimum
path
(MEP)
valley
ridge
inflection
point
but
not
based
transformation
intrinsic
bond
orbitals.
Despite
this,
minor
formed
MEP,
even
an
surface,
following
more
asynchronous
yet
concerted
mechanism.
overall
decisive
for
stabilization
TS
determining
selectivity
or
bifurcated
pathways
emergence
ambimodal
character.
Язык: Английский
Protonation pattern as a controlling factor of thermal reactions of aryl o-divinylbenzenes in acidic media: an integrated experimental–theoretical study
Reaction Chemistry & Engineering,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
The
thermal
transformations
of
various
thienyl
and
phenyl
derivatives
o
-divinylbenzene
in
acidic
media
were
investigated
an
integrated
experimental–theoretical
study.
Язык: Английский
With a little help from our (AI) friend: A general transition state sampling method for tropospheric hydrogen abstraction reactions
Atmospheric Environment,
Год журнала:
2024,
Номер
328, С. 120515 - 120515
Опубликована: Апрель 15, 2024
Due
to
their
pivotal
role
in
atmospheric
processes,
hydrogen
abstraction
reactions
are
vital
the
study
of
tropospheric
chemistry.
In
this
work,
we
present
an
algorithm
that
generates
a
large
number
chemically
sound
geometries
for
optimization
transition
states
(TSs)
bimolecular
H
reactions.
The
code,
which
was
developed
early
stages
with
help
artificial
intelligence
(AI),
automatically
detects
active
atoms
molecule
and
can
be
used
OH,
Cl,
NO3
oxidants.
Given
ubiquity
transfer
various
fields,
designed
general
terms
facilitate
easy
adaptation
other
oxidants,
thus
allowing
broader
range
applications.
As
result
its
use,
much
greater
TSs
is
predicted
when
compared
previous
theoretical
studies
six
oxidation
addition
improving
our
understanding
H-abstraction
process,
obtaining
increased
also
fundamentally
important
calculating
more
accurate
rate
constants
lifetimes
volatile
organic
compounds.
simplicity
significance
such
tool
context
environmental
chemistry
should
make
it
appealing
researchers
all
backgrounds.
Язык: Английский