A Theoretical Study of the Bifurcation Reaction II : Acetic Acid
Reads0
Chats0
TLDR
In this paper, the authors examined the competing reactions in the thermal unimolecular decomposition of acetic acid and showed that the potential barrier heights were mostly the same for the two competing reaction paths.Abstract:
The competing reactions in the thermal unimolecular decomposition of acetic acid were examined theoretically. Calculations of the transition state structures, the activation energies, and the intrinsic reaction coordinates (IRC) for the two competing reaction paths were performed by using the molecular orbital and the density functional theory. The potential barrier heights were mostly the same for the two competing reaction paths, which were consistent with previous studies. An examination of the mode coupling between the IRC and vibrational modes predicted no significant difference in the rates for the corresponding paths in agreement with experimental results. This is different from the case of formic acid which was reported in our previous paper of this series. The unimolecular reaction rate seems to be controlled by the number of effective vibrational modes which couple strongly with the IRC before the reactant arrives at the transition state.read more
Figures
Citations
More filters
Journal ArticleDOI
Mechanisms of Propylene Glycol and Triacetin Pyrolysis
TL;DR: The thermal decomposition mechanisms found theoretically for propylene glycol and triacetin were validated by a qualitative experimental investigation using gas-phase chromatography-mass spectroscopy, with excellent agreement.
Journal ArticleDOI
Unimolecular decomposition of formic acid in the gas phase--on the ratio of the competing reaction channels.
TL;DR: The thermal decomposition of formic acid was reinvestigated in the gas phase using two types of shock tubes and it was confirmed that the unimolecular decomposition proceeds through a main channel of dehydration and a minor decarboxylation channel.
Journal ArticleDOI
Laminar burning velocity of acetic acid + air flames
TL;DR: In this article, a detailed reaction mechanism for acetic acid combustion was developed and measured in non-stretched flames, stabilized on a perforated plate burner at adiabatic conditions.
Journal ArticleDOI
Sunlight-Initiated Photochemistry: Excited Vibrational States of Atmospheric Chromophores
TL;DR: In this article, the authors present an alternative process by which chemical reactions occur with the excitation of vibrational levels in the ground electronic state by red solar photons, focusing on the O-H vibrational manifold which can be an atmospheric chromophore for driving vibrationally mediated overtone-induced chemical reactions.
References
More filters
Journal ArticleDOI
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
TL;DR: Numerical calculations on a number of atoms, positive ions, and molecules, of both open- and closed-shell type, show that density-functional formulas for the correlation energy and correlation potential give correlation energies within a few percent.
Journal ArticleDOI
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
TL;DR: In this paper, a detailed study of correlation effects in the oxygen atom was conducted, and it was shown that primitive basis sets of primitive Gaussian functions effectively and efficiently describe correlation effects.
Journal ArticleDOI
Density-functional thermochemistry. I. The effect of the exchange-only gradient correction
TL;DR: In this paper, an extensive survey of density functional atomization energies on the 55 molecules of the Gaussian-1 thermochemical data base of Pople and co−workers is presented.