A Theoretical Study of the Bifurcation Reaction of Formic Acid : Dynamics around the Intrinsic Reaction Coordinate

Journal of Molecular Structure : THEOCHEM Volume 545 Issue 1 Page 197-205 published_at 2001-07-09
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Title ( eng )
A Theoretical Study of the Bifurcation Reaction of Formic Acid : Dynamics around the Intrinsic Reaction Coordinate
Creator
Itoh Kuniharu
Kawano Akio
Saito Ko
Source Title
Journal of Molecular Structure : THEOCHEM
Volume 545
Issue 1
Start Page 197
End Page 205
Abstract
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.
Keywords
formic acid
thermal decomposition
bifurcation reaction
IRC
reaction-path Hamiltonian
NDC
Chemistry [ 430 ]
Language
eng
Resource Type journal article
Publisher
Elsevier
Date of Issued 2001-07-09
Rights
Copyright (c) 2001 Elsevier Ltd.
Publish Type Author’s Original
Access Rights open access
Source Identifier
[ISSN] 0166-1280
[DOI] 10.1016/S0166-1280(01)00406-7
[NCID] AA11533429
[DOI] http://dx.doi.org/10.1016/S0166-1280(01)00406-7 isVersionOf