大气中硫酸生成反应势能面的量子化学研究

A new potential energy surface (PES) for the atmospheric formation of sulfuric acid from OH+SO₂ is investigated using density functional theory and high-level ab initio molecular orbital theory. A pathway focused on the new PES assumes the reaction to take place between the radical complex SO₃·HO₂ and H₂O. The unusual stability of SO₃·HO₂ is the principal basis of the new pathway, which has the same final outcome as the current reaction mechanism in the literature but it avoids the production and complete release of SO₃. The entire reaction pathway is composed of three consecutive elementary steps:(1) HOSO₂+O₂→SO₃·HO₂, (2) SO₃·HO₂+H₂O→SO₃·H₂O·HO₂, (3) SO₃·H₂O·HO₂→H₂SO₄+HO₂. All three steps have small energy barriers, under 10 kcal/mol, and are exothermic, and the new pathway is therefore favorable both kinetically and thermodynamically. As a key step of the reactions, step (3), HO₂ serves as a bridge molecule for low-barrier hydrogen transfer in the hydrolysis of SO₃. Two significant atmospheric implications are expected from the present study. First, SO₃ is not released from the oxidation of SO₂ by OH radical in the atmosphere. Second, the conversion of SO₂ into sulfuric acid is weakly dependent on the humidity of air.

Quantum Chemical Study of Potential Energy Surface in the Formation of Atmospheric Sulfuric Acid