The enhancement mechanism of glycolic acid on the formation of atmospheric sulfuric acid–ammonia molecular clusters

Abstract

Highly oxidized multifunctional organic molecules, which span a wide range of low volatilities, are capable of driving particle formation as well as the initial growth of particles in the atmosphere. However, their participant mechanism in new particle formation still remains largely ambiguous. Here we present an investigation of the potentially participant mechanism of the simplest hydroxyl acid, glycolic acid (GA) on clusters formation by sulfuric acid (SA) and ammonia (A). Density functional theory calculations at the M062X/6-311++G(3df,3pd) level of theory combining with atmospheric cluster dynamics code simulations of (𝐒𝐀)x⋅𝐀y⋅(𝐆𝐀)z cluster (y≤x + z ≤ 3) systems at different temperatures (298, 278, 258, 238, and 218 K) give direct evidence of the enhancement effect of GA on the formation rates of SA-A-based clusters at high concentration of GA and T = 238 K and 218 K. Moreover, within GA’s enhancement concentrations, the enhancement strength R of GA presents a positive dependence on its atmospheric concentrations and a negative dependence on temperature. A competitive relationship between SA and GA has been identified through the negative dependence of R on the concentrations of SA. The influence of A on R is more complex that R first increases, reaching a maximum value, and then decreases with the increasing concentration of A. Finally, the combination of the traced growth paths of the system with the enhancement strength of GA suggests a “catalytic” enhancement mechanism of GA where GA acts as a mediate bridge for the formation of pure SA-A-based clusters.