International Journal of Molecular Sciences,
Год журнала:
2025,
Номер
26(11), С. 5062 - 5062
Опубликована: Май 24, 2025
This
study
employs
time-dependent
density
functional
theory
to
explore
the
photophysical
properties
of
a
chiral
iridium(III)
complex
designed
as
photosensitizer
for
photodynamic
therapy.
Key
analyzed
include
one-photon
absorption
energies,
singlet–triplet
energy
gaps,
spin–orbit
coupling
constants,
and
intersystem
crossing
rate
constants.
The
potential
operation
in
Type
I
PDT
mechanism
was
assessed
through
ionization
electron
affinity
calculations.
results
demonstrate
that
is
promising
candidate,
primarily
operating
II
mechanism,
while
offering
conditional
viability
photoreactivity
under
specific
electronic
environmental
conditions.
Inorganics,
Год журнала:
2025,
Номер
13(2), С. 57 - 57
Опубликована: Фев. 15, 2025
A
series
of
mononuclear
complexes,
[Fe(L5)(bylim)](BPh4),
where
L5
represents
a
pentadentate
Schiff
base
ligand,
bylim
is
1-benzyl-1-imidazole,
and
BPh4−
the
tetraphenylborate
anion,
was
synthesized.
The
determined
crystal
structures
indicate
absence
significant
cooperative
interactions,
which
influence
properties
eventual
spin
transition.
Changes
in
magnetic
behavior
induced
by
substitution
ligand
were
investigated
through
susceptibility
measurements.
It
found
that
only
complexes
containing
non-substituted
secondary
amino
group
exhibit
some
form
crossover,
whereas
majority
those
with
methyl
substituent
remain
high-spin
state
across
entire
measured
temperature
range
(2–300
K).
changes
amine
further
explored
theoretical
calculations
at
DFT
CASSCF/NEVPT2
levels
theory.
topology
energetics
electron
density
atomic
charges
QT-AIM
calculations.
The Journal of Chemical Physics,
Год журнала:
2025,
Номер
162(16)
Опубликована: Апрель 22, 2025
Density
functional
theory
(DFT)
thermochemistry
of
3d
transition-metal
complexes
is
well-known
to
be
sensitive
the
amount
exact
Hartree–Fock
exchange
incorporated
into
exchange–correlation
functional.
For
example,
relative
energies
different
protonation
states
iron–sulfur
may
vary
by
hundreds
kJ/mol
among
DFT
methods.
In
present
study,
we
examine
four
isomers
[CH3S4Fe2IIIS2H]−
[2Fe–2S]
ferredoxin
model.
Compared
many-body
ab
initio
phaseless
auxiliary-field
quantum
Monte
Carlo
with
multi-Slater
determinant
trial
wavefunctions
and
fully
connected
singles
doubles
coupled-cluster
perturbative
triples
methods,
r2SCAN12-D4,
B3LYP-D4,
B97-1-D3(OP)
approaches
perform
best.
We
also
demonstrate
that
density-corrected
on
top
KS-CCSD
electronic
densities
provides
reliable
results
r2SCAN
Moreover,
direct
random
phase
approximation
TPSSh,
O3LYP,
r2SCAN12
hybrid
functionals
performs
well.
Wiley Interdisciplinary Reviews Computational Molecular Science,
Год журнала:
2025,
Номер
15(2)
Опубликована: Март 1, 2025
ABSTRACT
Version
6.0
of
the
ORCA
quantum
chemistry
program
suite
was
released
in
July
2024.
is
a
major
turning
point
history
since
it
represents
near
complete
rewrite
code
base
that
leads
to:
(1)
performance
improvements,
(2)
clean
and
highly
efficient
greatly
facilitates
future
development,
(3)
large
amount
new
functionality,
(4)
interface
capabilities
facilitate
inter‐operability
with
other
packages.
The
article
describes
most
salient
features
program.
International Journal of Molecular Sciences,
Год журнала:
2025,
Номер
26(11), С. 5062 - 5062
Опубликована: Май 24, 2025
This
study
employs
time-dependent
density
functional
theory
to
explore
the
photophysical
properties
of
a
chiral
iridium(III)
complex
designed
as
photosensitizer
for
photodynamic
therapy.
Key
analyzed
include
one-photon
absorption
energies,
singlet–triplet
energy
gaps,
spin–orbit
coupling
constants,
and
intersystem
crossing
rate
constants.
The
potential
operation
in
Type
I
PDT
mechanism
was
assessed
through
ionization
electron
affinity
calculations.
results
demonstrate
that
is
promising
candidate,
primarily
operating
II
mechanism,
while
offering
conditional
viability
photoreactivity
under
specific
electronic
environmental
conditions.
