Quantum chemical modeling of atmospheric molecular clusters involving inorganic acids and methanesulfonic acid

Engsvang, M.; Wu, H.; Knattrup, Y.; Kubečka, J.; Jensen, A. Buchgraitz; Elm, J.

doi:10.1063/5.0152517

Cited by 10 publications

(11 citation statements)

References 209 publications

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“…In this study, we applied an electric field of strength ranging from |E| = 0.005 to 1.0 V Å −1 (1 Å = 10 −10 m) and used density functional theory (DFT) to examine how the field affects the structure and energetics of the water dimer, as well as bimolecular clusters of sulfuric acid (H 2 SO 4 ) with water, ammonia, dimethylamine (DMA, (CH 3 ) 2 NH), and the sulfuric acid dimer. These clusters represent the most important systems to consider in describing the initial stages of atmospheric NPF; 27−31 for recent reviews of this topic, see e.g., Elm et al 32 and/or Engsvang et al 33…”

Section: Introductionmentioning

confidence: 99%

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Effect of an Electric Field on the Structure and Stability of Atmospheric Clusters

Daub,

Kurtén

2024

J. Phys. Chem. A

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We study the influence of an applied electric field on the structure and stability of some common bimolecular clusters that are found in the atmosphere. These clusters play an important role in new particle formation (NPF). For low values of the electric field (i.e., |E| ≤ 0.01 V Å–1), we demonstrate that the field response of the clusters can be predicted from simply calculating the dipole moment of the cluster and the dipole moments of the constituent molecules and that the influence on the association energy of the cluster is minimal (i.e., <0.5 kcal mol–1). For higher field strengths |E| > 0.2 V Å–1, there can be more dramatic effects on both structure and energetics, as the induced dipole, charge transfer, and geometric distortion play a larger role. Although such large fields are not very relevant in the atmosphere, they do exist in some situations of experimental interest, such as near interfaces and in intense laser fields.

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Section: Introductionmentioning

confidence: 99%

“…These clusters represent the most important systems to consider in describing the initial stages of atmospheric NPF; − for recent reviews of this topic, see e.g., Elm et al . and/or Engsvang et al…”

Section: Introductionmentioning

confidence: 99%

Effect of an Electric Field on the Structure and Stability of Atmospheric Clusters

Daub,

Kurtén

2024

J. Phys. Chem. A

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“…Recent studies have shown the contribution of iodine oxyacids to particle formation in the Arctic, − both due to their abundance and their binding affinity with nucleation precursors such as SA, DMA, TMA, and others. Therefore, we speculate that other halogen oxyacids could also be potential contributors if they are present.…”

Section: Introductionmentioning

confidence: 99%

Chlorine Oxyacids Potentially Contribute to Arctic Aerosol Formation

Engsvang,

Knattrup,

Kubečka

et al. 2024

Environ. Sci. Technol. Lett.

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To understand Arctic amplification, it is necessary to understand both the direct and indirect aerosol effect. Especially the indirect aerosol effect is important, due to the low background level of cloud condensation nuclei in the Arctic. Previous studies have shown how iodine oxyacids can contribute to the formation of aerosols in marine and polar areas, and we speculate that chlorine oxyacids, if present, could also contribute to particle formation. Recent measurements have observed the presence of chloric (CA) and perchloric acid (PA) in significant concentrations in the Arctic. Using quantum chemical methods, we have studied the (acid) 0−2 (base) 0−2 clusters, where the acid denotes CA, PA, or sulfuric acid (SA) and the base denotes ammonia, methylamine, dimethylamine, or trimethylamine. This allowed us to simulate the cluster formation potential of the chemical species. We found PA to have a high nucleation potential but, due to low concentrations, should only be present as a minor constituent of nucleating clusters. However, at low temperatures during high concentration events, it can become a substantial additional contribution to SA-driven nucleation. Therefore, further measurements and studies of larger multicomponent clusters should be pursued in order to constrain the potential contribution of PA to Arctic nucleation.

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“…In general, it has been found that sulfuric acid (SA) and bases, such as ammonia (AM) − and alkylamines, − form strongly bound clusters. The stability of SA–base clusters has been found to correlate with the basicity of the base for small cluster sizes. , In addition, it has been found that SA–base clusters are most stable when they consist of an equal number of SA and base molecules, i.e., a 1:1 ratio. , We refer to our recent reviews on organic and inorganic cluster formation for a comprehensive overview of studied cluster systems in the literature.…”

Section: Introductionmentioning

confidence: 99%

“… 16 , 17 In addition, it has been found that SA–base clusters are most stable when they consist of an equal number of SA and base molecules, i.e., a 1:1 ratio. 18 , 19 We refer to our recent reviews on organic 20 and inorganic 21 cluster formation for a comprehensive overview of studied cluster systems in the literature.…”

Section: Introductionmentioning

confidence: 99%

Improved Configurational Sampling Protocol for Large Atmospheric Molecular Clusters

Wu,

Engsvang,

Knattrup

et al. 2023

ACS Omega

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The nucleation process leading to the formation of new atmospheric particles plays a crucial role in aerosol research. Quantum chemical (QC) calculations can be used to model the early stages of aerosol formation, where atmospheric vapor molecules interact and form stable molecular clusters. However, QC calculations heavily depend on the chosen computational method, and when dealing with large systems, striking a balance between accuracy and computational cost becomes essential. We benchmarked the binding energies and structures and found the B97-3c method to be a good compromise between the accuracy and computational cost for studying large cluster systems. Further, we carefully assessed configurational sampling procedures for targeting large atmospheric molecular clusters containing up to 30 molecules (approximately 2 nm in diameter) and proposed a funneling approach with highly improved accuracy. We find that several parallel ABCluster explorations lead to better guesses for the cluster global energy minimum structures than one long exploration. This methodology allows us to bridge computational studies of molecular clusters, which typically reach only around 1 nm, with experimental studies that often measure particles larger than 2 nm. By employing this workflow, we searched for low-energy configurations of large sulfuric acid–ammonia and sulfuric acid–dimethylamine clusters. We find that the binding free energies of clusters containing dimethylamine are unequivocally more stable than those of the ammonia-containing clusters. Our improved configurational sampling protocol can in the future be applied to study the growth and dynamics of large clusters of arbitrary compositions.

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Quantum chemical modeling of atmospheric molecular clusters involving inorganic acids and methanesulfonic acid

Cited by 10 publications

References 209 publications

Effect of an Electric Field on the Structure and Stability of Atmospheric Clusters

Effect of an Electric Field on the Structure and Stability of Atmospheric Clusters

Chlorine Oxyacids Potentially Contribute to Arctic Aerosol Formation

Improved Configurational Sampling Protocol for Large Atmospheric Molecular Clusters

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