The Journal of Physical Chemistry Letters,
Год журнала:
2024,
Номер
unknown, С. 12628 - 12635
Опубликована: Дек. 17, 2024
Simplified
quantum
chemistry
(sQC)
methods
can
routinely
compute
excited
states
for
very
large
systems
in
an
"all-atom"
fashion.
They
are
viable
alternatives
to
regular
multiscale
schemes.
sQC
have
the
advantage
of
accounting
explicitly
all
environment
at
a
mechanical
(QM)
level.
The
treatment
charge-transfer
is
now
improved
by
native
implementation
range-separated
hybrid
(RSH)
exchange-correlation
functionals
into
eXact
integral
simplified
time-dependent
density
functional
theory
(XsTD-DFT).
After
RSH
XsTD-DFT/TDA
scheme
was
benchmarked,
XsTD-DFT(/TDA)
ultraviolet/visible
absorption,
circular
dichroism
(CD),
and/or
two-photon
absorption
(2PA)
spectra
were
directly
compared
results
experiments
four
challenging
and
increasingly
systems:
eYFP
model
system,
Λ-shaped
multimodular
D-π-A-π-D'-π-A-π-D
chromophore,
mixed
donor/acceptor
ligand
Pd(II)
double
cage
[3BF
We
present
the
largest
dataset
of
highly-accurate
vertical
and
degenerate
two-photon
transition
strengths
($\delta^{\mbox{\tiny
TPA}}$)
for
standard
small-
medium-sized
organic
molecules,
calculated
using
quadratic
response
implementation
third-order
coupled
cluster
method
that
includes
iterative
triples
(Q-CC3).
The
aug-cc-pVTZ
basis
set
was
used
all
small
while
molecules
were
assessed
with
aug-cc-pVDZ
differences
due
to
sets
are
discussed.
This
dataset,
encompassing
82
singlet
transitions
various
characters
(Rydberg,
valence,
double
excitations),
enables
a
comprehensive
benchmark
both
and,
alternative
wavefunction
methods
when
Q-CC3
calculations
become
beyond
reach.
These
include
(Q)
equation
motion
CCSD
approximations,
Q-CC2,
second-order
algebraic
diagrammatic
construction
in
its
intermediate
state
representation
(I-ADC2),
as
well
time-dependent
density
functional
theory
(TD-DFT)
5
commonly
exchange-correlation
functionals.
extensive
analysis
provides
quantitative
assessment
these
methods,
revealing
how
different
system
sizes,
intensities,
types
affect
their
performances.
The Journal of Physical Chemistry Letters,
Год журнала:
2024,
Номер
unknown, С. 12628 - 12635
Опубликована: Дек. 17, 2024
Simplified
quantum
chemistry
(sQC)
methods
can
routinely
compute
excited
states
for
very
large
systems
in
an
"all-atom"
fashion.
They
are
viable
alternatives
to
regular
multiscale
schemes.
sQC
have
the
advantage
of
accounting
explicitly
all
environment
at
a
mechanical
(QM)
level.
The
treatment
charge-transfer
is
now
improved
by
native
implementation
range-separated
hybrid
(RSH)
exchange-correlation
functionals
into
eXact
integral
simplified
time-dependent
density
functional
theory
(XsTD-DFT).
After
RSH
XsTD-DFT/TDA
scheme
was
benchmarked,
XsTD-DFT(/TDA)
ultraviolet/visible
absorption,
circular
dichroism
(CD),
and/or
two-photon
absorption
(2PA)
spectra
were
directly
compared
results
experiments
four
challenging
and
increasingly
systems:
eYFP
model
system,
Λ-shaped
multimodular
D-π-A-π-D'-π-A-π-D
chromophore,
mixed
donor/acceptor
ligand
Pd(II)
double
cage
[3BF
