Premium
Mechanism of the O 2 ( 1 Δ g ) generation from the Cl 2 /H 2 O 2 basic aqueous solution explored by the combined ab initio calculation and nonadiabatic dynamics simulation
Author(s) -
Wang YaTing,
Liu XiangYang,
Fang WeiHai
Publication year - 2019
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25713
Subject(s) - intersystem crossing , chemistry , aqueous solution , exothermic reaction , ab initio , quantum yield , singlet state , solvent , yield (engineering) , decomposition , computational chemistry , conical intersection , singlet oxygen , oxygen , molecule , excited state , thermodynamics , atomic physics , physics , quantum mechanics , fluorescence , organic chemistry
In the present work, mechanism of the O 2 ( 1 Δ g ) generation from the reaction of the dissolved Cl 2 with H 2 O 2 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 Δ 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 (Σ3 g − ) can be produced with considerable probability through nonadiabatic intersystem crossing in the 1 Δ g /Σ3 g − 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 Δ g ) generation. © 2018 Wiley Periodicals, Inc.