Theoretical studies on the electron capture properties of the H2SO4⋯HOO˙ complex and its implications as an alternative source of HOOH

Abstract

To better understand the potential role of sulfuric acid aerosols in the atmosphere, the electron capture properties of the H₂SO₄⋯HOO˙ complex have been systematically investigated by employing the MP2 and B3LYP methods in combination with the atoms in molecules (AIM) theory, energy decomposition analysis (EDA), and ab initio molecular dynamics. It was found that the electron capture process is a favorable reaction thermodynamically and kinetically. The excess electron can be captured by the HOO˙ fragment initially, and then the proton of the H₂SO₄ fragment associated with the intermolecular H-bonds is transferred to the HOO˙ fragment without any activation barriers, resulting in the formation of the HOOH species directly. Therefore, the electron capture process of the H₂SO₄⋯HOO˙ complex provides an alternative source of HOOH in the atmosphere. The nature of the coupling interactions in the electron capture products are clarified, and the most stable anionic complex is also determined. Additionally, the influences of the adjacent water molecules on the electron capture properties are investigated, as well as the distinct IR features of the most stable electron capture product.