The potential role of malonic acid in the atmospheric sulfuric acid - Ammonia clusters formation

Malonic acid (MOA), one of the major dicarboxylic acids (DCAs) in aerosols, has been identified experimentally and computationally to be a strong acid. However, its potential role in the atmospheric clusters formation is still ambiguous. Hence, the participant mechanism of MOA on the formation of atmospheric sulfuric acid (SA)- ammonia (A) clusters was investigated by combining computational methods with atmospheric cluster dynamics code (ACDC). The most stable molecular structures obtained at the M06-2X/6-311++G(3df,3pd) level of theory shows that the added MOA molecule in the SA-A-based clusters presents a promotion on the interactions between SA and A molecules. ACDC simulations indicate directly an obvious enhancement strength R_MOA on the clusters formation rates at 218 K and the concentration of MOA ([MOA]) larger than 10⁸ molecules cm⁻³, up to five orders of magnitude. Meanwhile, enhancement strength of MOA is compared with that of glycolic acid, and as expected, MOA presents a superior enhancement strength. Both R_MOA and the compared enhancement strength (r_com) present a positive dependency on [MOA] and a negative dependency on [SA]. With the increase of [A], both R_MOA and r_com (except at [SA] = 10⁴ molecules cm⁻³) first increase, reaching the maximum value and then decrease. Finally, a catalytic participant mechanism of MOA where MOA acts as a mediate bridge for the formation of pure SA-A-based clusters has been identified by tracing the main growth pathways of the system.