標題: Anharmonic effect of the unimolecular dissociation of CH3COOH
作者: Zhang, Liwei
Yao, Li
Li, Qian
Wang, Guiqiu
Lin, S. H.
應用化學系
Department of Applied Chemistry
關鍵字: anharmonic effect;isotopic effect;rate constant;RRKM method;unimolecular reaction
公開日期: 2-十一月-2014
摘要: Anharmonic and harmonic rate constants of the reactions have been calculated with the Rice-Ramsperger-Kassel-Marcus theory, and the anharmonic results are higher than the harmonic ones. The anharmonic effect and isotopic effect on the decomposition reactions have also been examined. The anharmonic effect in all the four reactions is obvious, especially at the high temperatures or energies. Relatively, the anharmonic effect on the reaction trans-acetic acid -> TS2 radical is the least obvious among the four reactions. In the microcanonical system, the difference of the rate constants between the deuterated results and the non-deuterated results is not negligible; in other words, the isotopic effect is obvious in all the four reactions. Among these reactions, three of the deuterated results (d, d3 and d4) have a big difference.
URI: http://dx.doi.org/10.1080/00268976.2014.915066
http://hdl.handle.net/11536/123921
ISSN: 0026-8976
DOI: 10.1080/00268976.2014.915066
期刊: MOLECULAR PHYSICS
Volume: 112
Issue: 21
起始頁: 2853
結束頁: 2871
顯示於類別:期刊論文


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