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

Abstract

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.