State-of-the-art local correlation methods enable affordable gold standard quantum chemistry for up to hundreds of atoms
Chemical Science,
Год журнала:
2024,
Номер
15(36), С. 14556 - 14584
Опубликована: Янв. 1, 2024
In
this
feature,
we
review
the
current
capabilities
of
local
electron
correlation
methods
up
to
coupled
cluster
model
with
single,
double,
and
perturbative
triple
excitations
[CCSD(T)],
which
is
a
gold
standard
in
quantum
chemistry.
The
main
computational
aspects
method
types
are
assessed
from
perspective
applications,
but
focus
kept
on
how
achieve
chemical
accuracy
(
Язык: Английский
Mechanism of the Visible-Light-Promoted C(sp3)–H Oxidation via Uranyl Photocatalysis
Inorganic Chemistry,
Год журнала:
2024,
Номер
63(5), С. 2418 - 2430
Опубликована: Янв. 24, 2024
Uranyl
cation,
as
an
emerging
photocatalyst,
has
been
successfully
applied
to
synthetic
chemistry
in
recent
years
and
displayed
remarkable
catalytic
ability
under
visible
light.
However,
the
molecular-level
reaction
mechanisms
of
uranyl
photocatalysis
are
unclear.
Here,
we
explore
mechanism
stepwise
benzylic
C-H
oxygenation
typical
alkyl-substituted
aromatics
(i.e.,
toluene,
ethylbenzene,
cumene)
via
using
theoretical
experimental
methods.
Theoretical
calculation
results
show
that
most
favorable
path
for
photocatalytic
oxidation
is
follows:
first,
hydrogen
atom
transfer
(HAT)
from
benzyl
position
form
a
carbon
radical
([R
Язык: Английский
Theoretical Insight on the Formation Mechanism of a Trisubstituted Derivative of Closo-Decaborate Anion [B10H7O2CCH3(NCCH3)]0
Inorganics,
Год журнала:
2023,
Номер
11(5), С. 201 - 201
Опубликована: Май 6, 2023
A
theoretical
modelling
of
the
interaction
process
between
a
protonated
complex
carboxonium
derivative
[2,6-B10H8O2CCH3*Hfac]0
and
acetonitrile
molecule
CH3CN
was
carried
out.
As
result
process,
trisubstituted
[B10H7O2CCH3(NCCH3)]0
formed.
This
reaction
has
an
electrophile-induced
nucleophilic
substitution
(EINS)
mechanism.
The
main
intermediates
transition
states
were
established.
in
case
all
previously
investigated
EINS
processes,
key
intermediate
anion
with
dihydrogen
H2
fragment
attached
to
one
boron
atom
(B(H2)
structure
motif).
can
proceed
on
different
position
cluster
cage.
potential
pathways
assessed.
It
established
that
B4
cage
most
energetically
favourable,
[2,4,6-B10H7O2CCH3(NCCH3)]0
isomer
Язык: Английский