Contribution of Methanesulfonic Acid to the Formation of Molecular Clusters in the Marine Atmosphere

Freja Rydahl Rasmussen; Jakub Kubecka; Jonas Elm

doi:10.1021/acs.jpca.2c04468

Contribution of Methanesulfonic Acid to the Formation of Molecular Clusters in the Marine Atmosphere

Freja Rydahl Rasmussen, Jakub Kubecka, Jonas Elm^*

^*Corresponding author for this work

Department of Chemistry
iCLIMATE Aarhus University Interdisciplinary Centre for Climate Change - iCLIMATE Aarhus University Interdisciplinary Centre for Climate Change, Langelandsgade

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

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Abstract

Because of the lack of long-term measurements, new particle formation (NPF) in the marine atmosphere remains puzzling. Using quantum chemical methods, this study elucidates the cluster formation and further growth of sulfuric acid-methanesulfonic acid-dimethylamine (SA-MSA-DMA) clusters, relevant to NPF in the marine atmosphere. The cluster structures and thermochemical parameters of (SA) _n(MSA) _m(DMA) _l(n + m ≤ 4 and l ≤ 4) systems are calculated using density functional theory at the ωB97X-D/6-31++G(d,p) level of theory, and the single-point energies are calculated using high-level DLPNO-CCSD(T ₀)/aug-cc-pVTZ calculations. The calculated thermochemistry is used as input to the Atmospheric Cluster Dynamics Code (ACDC) to gain insight into the cluster dynamics. At ambient conditions (298.15 K, 1 atm), we find that the distribution of outgrowing clusters primarily consists of SA and DMA, with a minor contribution from the mixed SA-MSA-DMA clusters. At lower temperature (278.15 K, 1 atm) the distribution broadens, and clusters containing one or more MSA molecules emerge. These findings show that in the cold marine atmosphere MSA likely participates in atmospheric NPF.

Original language	English
Journal	The Journal of Physical Chemistry A
Volume	126
Issue	40
Pages (from-to)	7127–7136
Number of pages	10
ISSN	1089-5639
DOIs	https://doi.org/10.1021/acs.jpca.2c04468
Publication status	Published - Oct 2022

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10.1021/acs.jpca.2c04468

Contribution of Methane Sulfonic Acid to the For- mation of Molecular Clusters in the Marine AtmosphereAccepted manuscript, 7.62 MBLicence: CC BY

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title = "Contribution of Methanesulfonic Acid to the Formation of Molecular Clusters in the Marine Atmosphere",

abstract = "Because of the lack of long-term measurements, new particle formation (NPF) in the marine atmosphere remains puzzling. Using quantum chemical methods, this study elucidates the cluster formation and further growth of sulfuric acid-methanesulfonic acid-dimethylamine (SA-MSA-DMA) clusters, relevant to NPF in the marine atmosphere. The cluster structures and thermochemical parameters of (SA) n(MSA) m(DMA) l(n + m ≤ 4 and l ≤ 4) systems are calculated using density functional theory at the ωB97X-D/6-31++G(d,p) level of theory, and the single-point energies are calculated using high-level DLPNO-CCSD(T 0)/aug-cc-pVTZ calculations. The calculated thermochemistry is used as input to the Atmospheric Cluster Dynamics Code (ACDC) to gain insight into the cluster dynamics. At ambient conditions (298.15 K, 1 atm), we find that the distribution of outgrowing clusters primarily consists of SA and DMA, with a minor contribution from the mixed SA-MSA-DMA clusters. At lower temperature (278.15 K, 1 atm) the distribution broadens, and clusters containing one or more MSA molecules emerge. These findings show that in the cold marine atmosphere MSA likely participates in atmospheric NPF.",

author = "Rasmussen, {Freja Rydahl} and Jakub Kubecka and Jonas Elm",

year = "2022",

month = oct,

doi = "10.1021/acs.jpca.2c04468",

language = "English",

volume = "126",

pages = "7127–7136",

journal = "The Journal of Physical Chemistry A",

issn = "1089-5639",

publisher = "American Chemical Society",

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Contribution of Methanesulfonic Acid to the Formation of Molecular Clusters in the Marine Atmosphere. / Rasmussen, Freja Rydahl; Kubecka, Jakub ; Elm, Jonas.
In: The Journal of Physical Chemistry A, Vol. 126, No. 40, 10.2022, p. 7127–7136.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

TY - JOUR

T1 - Contribution of Methanesulfonic Acid to the Formation of Molecular Clusters in the Marine Atmosphere

AU - Rasmussen, Freja Rydahl

AU - Kubecka, Jakub

AU - Elm, Jonas

PY - 2022/10

Y1 - 2022/10

N2 - Because of the lack of long-term measurements, new particle formation (NPF) in the marine atmosphere remains puzzling. Using quantum chemical methods, this study elucidates the cluster formation and further growth of sulfuric acid-methanesulfonic acid-dimethylamine (SA-MSA-DMA) clusters, relevant to NPF in the marine atmosphere. The cluster structures and thermochemical parameters of (SA) n(MSA) m(DMA) l(n + m ≤ 4 and l ≤ 4) systems are calculated using density functional theory at the ωB97X-D/6-31++G(d,p) level of theory, and the single-point energies are calculated using high-level DLPNO-CCSD(T 0)/aug-cc-pVTZ calculations. The calculated thermochemistry is used as input to the Atmospheric Cluster Dynamics Code (ACDC) to gain insight into the cluster dynamics. At ambient conditions (298.15 K, 1 atm), we find that the distribution of outgrowing clusters primarily consists of SA and DMA, with a minor contribution from the mixed SA-MSA-DMA clusters. At lower temperature (278.15 K, 1 atm) the distribution broadens, and clusters containing one or more MSA molecules emerge. These findings show that in the cold marine atmosphere MSA likely participates in atmospheric NPF.

AB - Because of the lack of long-term measurements, new particle formation (NPF) in the marine atmosphere remains puzzling. Using quantum chemical methods, this study elucidates the cluster formation and further growth of sulfuric acid-methanesulfonic acid-dimethylamine (SA-MSA-DMA) clusters, relevant to NPF in the marine atmosphere. The cluster structures and thermochemical parameters of (SA) n(MSA) m(DMA) l(n + m ≤ 4 and l ≤ 4) systems are calculated using density functional theory at the ωB97X-D/6-31++G(d,p) level of theory, and the single-point energies are calculated using high-level DLPNO-CCSD(T 0)/aug-cc-pVTZ calculations. The calculated thermochemistry is used as input to the Atmospheric Cluster Dynamics Code (ACDC) to gain insight into the cluster dynamics. At ambient conditions (298.15 K, 1 atm), we find that the distribution of outgrowing clusters primarily consists of SA and DMA, with a minor contribution from the mixed SA-MSA-DMA clusters. At lower temperature (278.15 K, 1 atm) the distribution broadens, and clusters containing one or more MSA molecules emerge. These findings show that in the cold marine atmosphere MSA likely participates in atmospheric NPF.

UR - https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.2c04468

U2 - 10.1021/acs.jpca.2c04468

DO - 10.1021/acs.jpca.2c04468

M3 - Journal article

C2 - 36191242

SN - 1089-5639

VL - 126

SP - 7127

EP - 7136

JO - The Journal of Physical Chemistry A

JF - The Journal of Physical Chemistry A

IS - 40

ER -

Contribution of Methanesulfonic Acid to the Formation of Molecular Clusters in the Marine Atmosphere

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