Mechanism of the O-2((1)Delta(g)) generation from the Cl-2/H2O2 basic aqueous solution explored by the combined ab initio calculation and nonadiabatic dynamics simulation

作者：Wang, Ya-Ting; Liu, Xiang-Yang; Fang, Wei-Hai^*

来源：Journal of Computational Chemistry, 2019, 40(2): 447-455.

DOI：10.1002/jcc.25713

• singlet molecular oxygen
• ab initio calculation
• dynamic simulation
• solvent effect
• nonadiabatic effect

In the present work, mechanism of the O-2((1)Delta(g)) generation from the reaction of the dissolved Cl-2 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 O-2((1)Delta(g)) 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 O-2(sigma 3g-) can be produced with considerable probability through nonadiabatic intersystem crossing in the (1)Delta(g)/sigma 3g- 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 O-2((1)Delta(g)) generation.

• 出版日期2019-1-15
• 单位北京师范大学