標題: Anharmonic Rice-Ramsperger-Kassel-Marcus (RRKM) and product branching ratio calculations for the partially deuterated protonated water dimers: Dissociation and isomerization
作者: Song, Di
Su, Hongmei
Kong, Fan-ao
Lin, Sheng-Hsien
應用化學系分子科學碩博班
Institute of Molecular science
公開日期: 14-三月-2013
摘要: Partially deuterated protonated water dimers, H2O center dot H+ center dot D2O, H2O center dot D+ center dot HDO, and HDO center dot H+ center dot HDO, as important intermediates of isotopic labeled reaction of H3O+ + D2O, undergo direct dissociation and indirect dissociation, i.e., isomerization before the dissociation. With Rice-Ramsperger-Kassel-Marcus theory and ab initio calculations, we have computed their dissociation and isomerization rate constants separately under the harmonic and anharmonic oscillator models. On the basis of the dissociation and isomerization rate constants, branching ratios of two primary products, [HD2O+]/[H2DO+], are predicted under various kinetics models with the harmonic or anharmonic approximation included. The feasible kinetics model accounting for experimental results is shown to include anharmonic effect in describing dissociation, while adopting harmonic approximation for isomerization. Thus, the anharmonic effect is found to play important roles affecting the dissociation reaction, while isomerization rates are shown to be insensitive to whether the anharmonic or harmonic oscillator model is being applied. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4794152]
URI: http://dx.doi.org/10.1063/1.4794152
http://hdl.handle.net/11536/21385
ISSN: 0021-9606
DOI: 10.1063/1.4794152
期刊: JOURNAL OF CHEMICAL PHYSICS
Volume: 138
Issue: 10
結束頁: 
顯示於類別:期刊論文


文件中的檔案:

  1. 000316543400026.pdf