Methanesulfonic acid and iodous acid nucleation: a novel mechanism for marine aerosols

Wu, N. J.; An, Ning; Liu, Ling; Zu, Haotian; Liang, Dandan; Zhang, Xiuhui

doi:10.1039/d3cp01198d

Cited by 4 publications

(2 citation statements)

References 55 publications

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“…Iodine-containing compounds can be found in large concentrations in the atmosphere, especially in marine coastal environments but also in the Arctic and the Antarctic, − due to large emissions from the ocean surface. , High concentrations of iodine-containing compounds have been shown to correlate with high particle concentrations and have been shown to lead to new particle formation in the Arctic and marine environments. ,,, The contribution of iodine-containing compounds to NPF has previously been studied with computational methods, but the exact contribution to NPF remains poorly understood . These studies have focused primarily on the formation of clusters with iodic acid (HIO 3 ) and iodous acid (HIO 2 ), either by themselves − or in combination with other known nucleation precursors such as sulfuric acid, methanesulfonic acid, − ammonia, and dimethylamine. , These studies show that iodic acid paired with either ammonia or dimethylamine generally forms very stable clusters, which could contribute significantly to particle formation.…”

Section: Introductionmentioning

confidence: 99%

Iodine Clusters in the Atmosphere I: Computational Benchmark and Dimer Formation of Oxyacids and Oxides

Engsvang,

Wu,

Elm

2024

ACS Omega

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The contribution of iodine-containing compounds to atmospheric new particle formation is still not fully understood, but iodic acid and iodous acid are thought to be significant contributors. While several quantum chemical studies have been carried out on clusters containing iodine, there is no comprehensive benchmark study quantifying the accuracy of the applied methods. Here, we present the first study in a series that investigate the role of iodine species in atmospheric cluster formation. In this work, we have studied the iodic acid, iodous acid, iodine tetroxide, and iodine pentoxide monomers and their dimers formed with common atmospheric precursors. We have tested the accuracy of commonly applied methods for calculating the geometry of the monomers, thermal corrections of monomers and dimers, the contribution of spin−orbit coupling to monomers and dimers, and finally, the accuracy of the electronic energy correction calculated at different levels of theory. We find that optimizing the structures either at the ωB97X-D3BJ/aug-cc-pVTZ-PP or the M06-2X/aug-cc-pVTZ-PP level achieves the best thermal contribution to the binding free energy. The electronic energy correction can then be calculated at the ZORA-DLPNO−CCSD(T 0 ) level with the SARC-ZORA-TZVPP basis for iodine and ma-ZORA-def2-TZVPP for non-iodine atoms. We applied this methodology to calculate the binding free energies of iodine-containing dimer clusters, where we confirm the qualitative trends observed in previous studies. However, we identify that previous studies overestimate the stability of the clusters by several kcal/mol due to the neglect of relativistic effects. This means that their contributions to the currently studied nucleation pathways of new particle formation are likely overestimated.

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Section: Introductionmentioning

confidence: 99%

Iodine Clusters in the Atmosphere I: Computational Benchmark and Dimer Formation of Oxyacids and Oxides

Engsvang,

Wu,

Elm

2024

ACS Omega

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“…It was found that diethylamine (DEA) has the highest EP, and sulfur oxoacids also have a high EP on the nucleation with HIO 3 as the partner . However, for the nucleation with HIO 2 as the partner, only the enhancement from HIO 3 and methanesulfonic acid (MSA) has been investigated. ,, More importantly, the EP of the same compounds on the nucleation with HIO 3 as the partner cannot simply be extrapolated to the nucleation with HIO 2 as the partner, due to the different properties and behaviors of HIO 3 and HIO 2 in neutral iodine oxoacid nucleation . Thus, evaluating the EP of abundant precursors on the nucleation with HIO 2 as the partner is warranted.…”

Section: Introductionmentioning

confidence: 99%

HIO₃–HIO₂-Driven Three-Component Nucleation: Screening Model and Cluster Formation Mechanism

Zhang,

Ma,

Zhang

et al. 2023

Environ. Sci. Technol.

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Iodine oxoacids (HIO3 and HIO2)-driven nucleation has been suggested to efficiently contribute to new particle formation (NPF) in marine atmospheres. Abundant atmospheric nucleation precursors may further enhance HIO3–HIO2-driven nucleation through various multicomponent nucleation mechanisms. However, the specific enhancing potential (EP) of different precursors remains largely unknown. Herein, the EP-based screening model of precursors and enhancing mechanism of the precursor with the highest EP on HIO3–HIO2 nucleation were investigated. The formation free energies (ΔG), as critical parameters for evaluating EP, were calculated for the dimers of 63 selected precursors with HIO2. Based on the ΔG values, (1) a quantitative structure–activity relationship model was developed for evaluating ΔG of other precursors and (2) atmospheric concentrations of 63 (precursor)1(HIO2)1 dimer clusters were assessed to identify the precursors with the highest EP for HIO3–HIO2-driven nucleation by combining with earlier results for the nucleation with HIO3 as the partner. Methanesulfonic acid (MSA) was found to be one of the precursors with the highest EP. Finally, we found that MSA can effectively enhance HIO3–HIO2 nucleation at atmospheric conditions by studying larger MSA–HIO3–HIO2 clusters. These results augment our current understanding of HIO3–HIO2 and MSA-driven nucleation and may suggest a larger impact of HIO2 in atmospheric aerosol nucleation.

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Atmospheric implications of hydrogen bonding between methanesulfonic acid and 12 kinds of N-containing compounds

Chen,

Ma,

et al. 2024

Computational and Theoretical Chemistry

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Methanesulfonic acid and iodous acid nucleation: a novel mechanism for marine aerosols

Abstract: By seeding clouds, new particle formation (NPF) has a substantial impact on radiation balance, bio-geochemical cycles and global climate. Over oceans, both methanesulfonic acid (CH3S(O)2OH, MSA) and iodous acid (HIO2)...

Cited by 4 publications

References 55 publications

Iodine Clusters in the Atmosphere I: Computational Benchmark and Dimer Formation of Oxyacids and Oxides

Iodine Clusters in the Atmosphere I: Computational Benchmark and Dimer Formation of Oxyacids and Oxides

HIO₃–HIO₂-Driven Three-Component Nucleation: Screening Model and Cluster Formation Mechanism

Atmospheric implications of hydrogen bonding between methanesulfonic acid and 12 kinds of N-containing compounds

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Methanesulfonic acid and iodous acid nucleation: a novel mechanism for marine aerosols

Abstract: By seeding clouds, new particle formation (NPF) has a substantial impact on radiation balance, bio-geochemical cycles and global climate. Over oceans, both methanesulfonic acid (CH3S(O)2OH, MSA) and iodous acid (HIO2)...

Cited by 4 publications

References 55 publications

Iodine Clusters in the Atmosphere I: Computational Benchmark and Dimer Formation of Oxyacids and Oxides

Iodine Clusters in the Atmosphere I: Computational Benchmark and Dimer Formation of Oxyacids and Oxides

HIO3–HIO2-Driven Three-Component Nucleation: Screening Model and Cluster Formation Mechanism

Atmospheric implications of hydrogen bonding between methanesulfonic acid and 12 kinds of N-containing compounds

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Product

Resources

About

HIO₃–HIO₂-Driven Three-Component Nucleation: Screening Model and Cluster Formation Mechanism