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Gibbs energy of activation for thermal isomerization of (1Z)‐acetaldehyde hydrazone and (1Z)‐acetaldehyde N,N‐dimethylhydrazone by Gaussian‐4 theory and CCSD(T)/CBS computations
Author(s) -
Lu ShihI
Publication year - 2009
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21217
Subject(s) - acetaldehyde , isomerization , hydrazone , computation , gaussian , chemistry , gibbs free energy , computational chemistry , thermodynamics , medicinal chemistry , organic chemistry , physics , computer science , ethanol , algorithm , catalysis
In this article, we examined the Gibbs energy of activation for the Z/E thermal isomerization reaction of (1Z)‐acetaldehyde hydrazone and (1Z)‐acetaldehyde N,N‐dimethylhydrazone, at 298.15 K in the solvent of cyclohexane. We carried out computations employing both the Gaussian‐4 (G4) theory and the coupled cluster method using both single and double substitutions and triple excitations noniteratively, CCSD(T). The CCSD(T) energy is extrapolated to the complete basis set (CBS). We compared the calculated results to the available experimental observation. It appeared that both G4 and CCSD(T)/CBS computations overestimated the experimental value by as much as about 6 and 12 kcal/mol in the present two cases. We discussed possible sources of error and proposed the experimental kinetic data could be questionable. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009