標題: Matrix reorganization with intramolecular tunneling of H atom: Formic acid in Ar matrix
作者: Trakhtenberg, Leonid I.
Fokeyev, Anatoly A.
Zyubin, Alexander S.
Mebel, Alexander M.
Lin, S. H.
應用化學系
應用化學系分子科學碩博班
Department of Applied Chemistry
Institute of Molecular science
關鍵字: argon;Debye temperature;hydrogen;organic compounds;perturbation theory;reaction rate constants;rotational isomerism;vibrational states
公開日期: 14-Apr-2009
摘要: The intramolecular tunneling of hydrogen atom in formic acid HCOOH at low temperatures is considered based on literature experimental data on C-O internal rotation. The energetic and geometric parameters as well as vibrational frequencies for formic acid in cis and trans configurations surrounded by 12 Ar atoms are calculated in the frame of the MP2 approach with extended basis sets. The temperature and pressure dependence of the rate constant is analyzed taking into consideration the matrix reorganization for the Debye model of lattice motion. It has been shown that the available experimental data can be explained by the suggested matrix reorganization mechanism. Theoretical expressions for the temperature dependence of the rate constant agree well with the experimental data on the cis to trans tunneling reactions in formic acid with fitting parameters attaining reasonable values. A mechanism describing pressure dependence of the rate constant for H-atom intramolecular tunneling reactions is also proposed.
URI: http://dx.doi.org/10.1063/1.3111263
http://hdl.handle.net/11536/7369
ISSN: 0021-9606
DOI: 10.1063/1.3111263
期刊: JOURNAL OF CHEMICAL PHYSICS
Volume: 130
Issue: 14
結束頁: 
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