Application of pseudo-diabatic electronic states buried in Hartree-Fock wavefunctions to describe bond dissociation processes

作者：Murakami Tomonori; Ohta Katsuhisa^*

来源：Computational and Theoretical Chemistry, 2015, 1065: 1-6.

DOI：10.1016/j.comptc.2015.04.013

• Hartree-Fock
• Diabatic electronic states
• Ion-pair
• Biradical
• Bond dissociation

Pseudo-diabatic electronic states buried in Hartree-Fock (HF) wavefunctions are applied to describe bond dissociation processes. The limited variational freedom of HF wavefunctions turns to their own advantage to approximately describe the "diabatic" ionic-pair state or the diabatic biradical state. As an application of the pseudo-diabatic states, CH-bond dissociation processes of normal alkanes and their branched isomers are investigated. Reasonable relationships between the diabatic crossing energies and the number of alkyl substituents on a radical center are obtained in accordance with hyperconjugation theory.

• 出版日期2015-8-1