In the present work, mechanism of the O2(1Δg) generation from the reaction of the dissolved Cl2 with H2O2 in basic aqueous solution has been explored by the combined ab initio calculation and nonadiabatic dynamics simulation, together with different solvent models. Three possible pathways have been determined for the O2(1Δg) generation, but two of them are sequentially downhill processes until formation of the OOCl− complex with water, which are of high exothermic character. Once the complex is formed, singlet molecular oxygen is easily generated by its decomposition along the singlet‐state pathway. However, triplet molecular oxygen of O2( Σ3g− ) can be produced with considerable probability through nonadiabatic intersystem crossing in the 1Δg/ Σ3g− intersection region. It has been found that the coupled solvent, heavy‐atom, and nonadiabatic effects have an important influence on the quantum yield of the O2(1Δg) generation. © 2018 Wiley Periodicals, Inc.

中文翻译：

---

结合从头算计算和非绝热动力学模拟探索 Cl2 /H2 O2 碱性水溶液生成 O2 (1 Δg ) 的机理

在目前的工作中，通过结合 ab initio 计算和非绝热动力学模拟以及不同的溶剂模型，探索了溶解的 Cl2 与 H2O2 在碱性水溶液中反应生成 O2(1Δg) 的机制。已经确定了 O2(1Δg) 生成的三种可能途径，但其中两种是顺序下坡过程，直到与水形成 OOCl− 复合物，其具有高放热特性。一旦形成复合物，单线态分子氧很容易通过沿着单线态途径分解产生。然而，通过在 1Δg/ Σ3g- 交叉区域中的非绝热系统间交叉，可以产生 O2( Σ3g- ) 三重态分子氧的可能性很大。已经发现偶联溶剂、重原子、和非绝热效应对 O2(1Δg) 生成的量子产率有重要影响。© 2018 Wiley Periodicals, Inc.