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.
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.
Lu
Shih-I
SI
Department of Chemistry, Soochow University, 70 Lin-Shih Road, Taipei, 11102 Taiwan. shih_i_lu@hotmail.com
D003198:Computer Simulation; D006835:Hydrazones / Q000737:chemistry*; D008956:Models, Chemical; D011789:Quantum Theory; D013237:Stereoisomerism; D013696:Temperature; D013816:Thermodynamics
D006835:Hydrazones