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ID 17097
本文ファイル
著者
Itoh, Kuniharu
Kawano, Akio
Saito, Ko
キーワード
formic acid
thermal decomposition
bifurcation reaction
IRC
reaction-path Hamiltonian
NDC
化学
抄録(英)
Transition state structures, activation energies, and the intrinsic reaction coordinate (IRC) for the two decomposition paths of formic acid are studied using Hartree-Fock and density functional theory (DFT). Formic acid decomposes via the following competing paths; to: (1) H2O+CO and to (2) H2+CO2. Experimental results which were obtained by Saito et al. have shown that the rate constant of path (2) is smaller than that of path (1) by about forty times over the experimental temperature range. On the other hand, calculated results using high level ab initio calculations such as MP4/cc-pVQZ//B3LYP/cc-pVTZ show that the activation energies of paths (1) and (2) are comparable. Detailed examinations of the mode coupling between the vibrational modes and the IRC's suggest that the large difference in the rate constants between the two reaction paths is attributable to the difference in curvature of the potential energy surfaces for the reaction paths around the IRC.
掲載誌名
Journal of Molecular Structure : THEOCHEM
545巻
1号
開始ページ
197
終了ページ
205
出版年月日
2001-07-09
出版者
Elsevier
ISSN
0166-1280
NCID
出版者DOI
言語
英語
NII資源タイプ
学術雑誌論文
広大資料タイプ
学術雑誌論文
DCMIタイプ
text
フォーマット
application/pdf
著者版フラグ
author
権利情報
Copyright (c) 2001 Elsevier Ltd.
関連情報URL(IsVersionOf)
http://dx.doi.org/10.1016/S0166-1280(01)00406-7
部局名
理学研究科