高等学校化学学报2011，Vol.32Issue(7)：1588-1593,6.
乙醇醛光解离机理的理论研究
Theoretical Studies on Photodissociation Mechanism of Glycoladehyde
摘要
Abstract
The electronic structures of the stationary points and dissociation potential energy surfaces ( PES) of glycolaldehyde(HOCH2CHO) in the lowest three electronic states (S0, S1 and T1 ) were calculated at the CASPT2//CASSCF/6-311 +G(2df, 2p) level of the multi-reference state method. Combining with the surface intersection points, the wavelength-dependent photolysis mechanisms leading to probable photolysis products were elucidated. It is shown that in the experimental photolysis wavelength range of 240-400 nm, the HOCH2CHO molecule mainly occurs the dissociation reactions on the S, surface or decays to the ground state via the S0 and S1 vibronic interaction, followed by S0 dissociation reactions. The C-C bond fission to yield ground-state products HOCH2(2A') + HCO(2A') is the dominant pathway, while in the certain wavelength range, the S0 concerted channel to produce CH3OH(A') + CO(A1 ) , H-elimination of the aldehyde group and OH-elimination channels are also energetically accessible. The present calculated results show good agreement with the experimental observations.关键词
反应机理/乙醇醛/光解离/势能面Key words
Reaction mechanism/Glycolaldehyde/Photodissociation/Potential energy surface分类
化学化工引用本文复制引用
慈成刚,段雪梅,刘靖尧,孙家钟..乙醇醛光解离机理的理论研究[J].高等学校化学学报,2011,32(7):1588-1593,6.基金项目
国家自然科学基金(批准号:20303007,20973077)和教育部新世纪优秀人才支持计划(NCET)资助. （批准号:20303007,20973077）
