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Ab initio study on the reaction mechanism of ozone with bromine atom
Author(s) -
Bing Dan,
Zhao Yongfang,
Hao Fengyou,
Li Xinying,
Liu Fengli,
Zhang Guohua,
Zhang Pingxia
Publication year - 2006
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21249
Subject(s) - bromine , chemistry , ab initio , halogen , transition state , reaction mechanism , ozone , atom (system on chip) , computational chemistry , potential energy surface , ab initio quantum chemistry methods , oxygen atom , photochemistry , molecule , catalysis , organic chemistry , computer science , embedded system , alkyl
Ab initio calculations of the potential energy surface (PES) for the Br+O 3 reaction have been performed using the MP2, CCSD(T), and QCISD(T) methods with 6‐31G( d ), 6‐311G( d ), and 6‐311+G(3 df ). The reaction begins with a transition state (TS) when the Br atom attacks a terminal oxygen of ozone, producing an intermediate, the bromine trioxide (M), which immediately dissociates to BrO+O 2 . The geometry optimizations of the reactants, products, and intermediate and transition states are carried out at the MP2/6‐31G( d ) level. The reaction potential barrier is 3.09 kcal/mol at the CCSD(T)/6‐311+G(3 df )//MP2 level, which shows that the bromine atom trends intensively to react with the ozone. The comparison of the Br+O 3 reaction with the F+O 3 and Cl+O 3 reactions indicates that the reactions of ozone with the halogen atoms have the similar reaction mechanism. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007