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Clusteromics II: Methanesulfonic Acid-Base Cluster Formation.

ABSTRACT: The role of methanesulfonic acid (MSA) in atmospheric new particle formation remains highly uncertain. Using state-of-the-art computational methods, we study the electrically neutral (MSA)_0-2(base)_0-2 clusters, with base = ammonia (A), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), and ethylenediamine (EDA). The cluster configurations are obtained using the ABCluster program and the number of initial cluster configurations is reduced based on PM7 calculations. Thermochemical parameters are calculated using the quasi-harmonic approximation based on the ωB97X-D/6-31++G(d,p) cluster structures and vibrational frequencies. The single point energies are calculated at the DLPNO-CCSD(T₀)/aug-cc-pVTZ level of theory. We find that MSA shows a different interaction pattern with the bases compared to sulfuric acid and does not simply follow the basicity of the bases for these small clusters. In all cases, we find that the MSA-base clusters show very low cluster formation potential, indicating that electrically neutral clusters consisting solely of MSA as the clustering acid are most likely not capable of forming and growing under realistic atmospheric conditions.

SUBMITTER: Elm J

PROVIDER: S-EPMC8264942 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Clusteromics III: Acid Synergy in Sulfuric Acid-Methanesulfonic Acid-Base Cluster Formation.

Project description:Acid-base molecular clusters are an important stage in atmospheric new particle formation. While such clusters are most likely multicomponent in nature, there are very few reports on clusters consisting of multiple acid molecules and multiple base molecules. By applying state-of-the-art quantum chemical methods, we herein study electrically neutral (SA)1(MSA)1(base)0-2 clusters with base = ammonia (A), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA) and ethylenediamine (EDA). The cluster structures are obtained using a funneling approach employing the ABCluster program, semiempirical PM7 calculations and ωB97X-D/6-31++G(d,p) calculations. The final binding free energies are calculated at the DLPNO-CCSD(T0)/aug-cc-pVTZ//ωB97X-D/6-31++G(d,p) level of theory using the quasi-harmonic approximation. Based on the calculated cluster geometries and thermochemistry (at 298.15 K and 1 atm), we find that the mixed (SA)1(MSA)1(base)1-2 clusters more resemble the (SA)2(base)1-2 clusters compared to the (MSA)2(base)1-2 clusters. Hence, some of the steric hindrance and lack of hydrogen bond capacity previously observed in the (MSA)2(base)1-2 clusters is diminished in the corresponding (SA)1(MSA)1(base)1-2 clusters. Cluster kinetics simulations reveal that the presence of an MSA molecule in the clusters enhances the cluster formation potential by up to a factor of 20. We find that the SA-MSA-DMA clusters have the highest cluster formation potential, and thus, this system should be further extended to larger sizes in future studies.

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