Quaternary Nucleation of Iodine and Sulfur Oxoacids in the Marine Atmosphere: Unexpected Role of Methanesulfonic Acid
Journal of Geophysical Research Atmospheres,
Год журнала:
2025,
Номер
130(8)
Опубликована: Апрель 17, 2025
Abstract
Sulfuric
acid
(SA),
methanesulfonic
(MSA),
iodic
(HIO
3
),
and
iodous
2
)
are
identified
as
key
nucleation
precursors
can
coexist
in
the
marine
atmosphere.
Here,
we
investigated
potential
SA‐MSA‐HIO
‐HIO
quaternary
mechanism
by
exploring
formation
of
(SA)
w
(MSA)
x
y
z
(0
≤
+
3,
1
3)
clusters
with
quantum
chemical
calculation
kinetics
modelling.
The
results
indicate
that
effectively
nucleate
under
atmospheric
conditions.
rate
is
up
to
7
orders
magnitude
higher
than
SA/MSA‐HIO
,
ternary
mechanisms,
SA/MSA/HIO
binary
mechanisms
at
some
specific
mainly
driven
acid‐base
reaction
base)
halogen
bonds
besides
hydrogen
bonds,
three
acids
showing
both
competitive
cooperative
roles.
More
importantly,
it
was
found
contribution
MSA
aerosol
comparable
SA
equal
concentrations.
unexpectedly
high
attributed
its
halogen‐bonding
capacity
SA.
This
study
highlights
need
consider
multicomponent
atmosphere
for
accurate
climate
projections,
may
serve
important
proof
weak
even
coexisting
Язык: Английский
Iodine Clusters in the Atmosphere I: Computational Benchmark and Dimer Formation of Oxyacids and Oxides
ACS Omega,
Год журнала:
2024,
Номер
9(29), С. 31521 - 31532
Опубликована: Июль 9, 2024
The
contribution
of
iodine-containing
compounds
to
atmospheric
new
particle
formation
is
still
not
fully
understood,
but
iodic
acid
and
iodous
are
thought
be
significant
contributors.
While
several
quantum
chemical
studies
have
been
carried
out
on
clusters
containing
iodine,
there
no
comprehensive
benchmark
study
quantifying
the
accuracy
applied
methods.
Here,
we
present
first
in
a
series
that
investigate
role
iodine
species
cluster
formation.
In
this
work,
studied
acid,
tetroxide,
pentoxide
monomers
their
dimers
formed
with
common
precursors.
We
tested
commonly
methods
for
calculating
geometry
monomers,
thermal
corrections
dimers,
spin–orbit
coupling
finally,
electronic
energy
correction
calculated
at
different
levels
theory.
find
optimizing
structures
either
ωB97X-D3BJ/aug-cc-pVTZ-PP
or
M06-2X/aug-cc-pVTZ-PP
level
achieves
best
binding
free
energy.
can
then
ZORA-DLPNO–CCSD(T0)
SARC-ZORA-TZVPP
basis
ma-ZORA-def2-TZVPP
non-iodine
atoms.
methodology
calculate
energies
dimer
clusters,
where
confirm
qualitative
trends
observed
previous
studies.
However,
identify
overestimate
stability
by
kcal/mol
due
neglect
relativistic
effects.
This
means
contributions
currently
nucleation
pathways
likely
overestimated.
Язык: Английский
Sulfuric Acid-Driven Nucleation Enhanced by Amines from Ethanol Gasoline Vehicle Emission: Machine Learning Model and Mechanistic Study
Environmental Science & Technology,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 5, 2024
The
sulfuric
acid
(SA)-amine
nucleation
mechanism
gained
increasing
attention
due
to
its
important
role
in
atmospheric
secondary
particle
formation.
However,
the
intrinsic
enhancing
potential
(IEP)
of
various
amines
remains
largely
unknown,
restraining
assessment
on
SA-amines
at
locations.
Herein,
machine
learning
(ML)
models
were
constructed
for
high-throughput
prediction
IEP
amines,
and
specific
with
high
was
investigated.
formation
free
energy
(Δ
Язык: Английский