Elsevier

Computers & Chemistry

Volume 19, Issue 3, September 1995, Pages 145-154
Computers & Chemistry

Workshop on computational methods for large molecular systems
Applications of the adiabatic connection method to conformational equilibria and reactions involving formic acid☆

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Abstract

Density Functional Theory (DFT) was used in this paper to study the conformational equilibria, vibrational spectra and reactions involving formic acid. The purpose of this study is two-fold: to resolve experimental discrepancies and to compare DFT results with high level ab initio results. First, we investigated structures and vibrational properties of trans and cis conformers of formic acid. We examined two unimolecular dissociation reactions and one internal rearrangement reaction. Local (LSD), non-local (NLSD) and the latest adiabatic connection (ACM) density functional approaches have been used. The barrier heights to the above mentioned reactions including zero point vibrational energy corrections were calculated and are in agreement with high level CCSDT-1 ab initio and the latest experimental results. In general, the ACM functional provides better geometries and reaction energetics than the BP86 non-local functional studied.

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    • ☆

    Workshop on Computational Methods for Large Molecular Systems, Technical University of Wrocław, 23–26 June 1994, Edited by Morris Krauss and W. Andrzej Sokalski.

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