Energy component analysis of the Jahn–Teller effect in the methane radical cation

Abstract

Extensive configuration-interaction calculations with double-zeta plus polarization and near triple-zeta plus polarization basis sets are used to analyze the Jahn–Teller (JT) effect in the methane radical cation. Energy component analysis shows that the Jahn–Teller effect leads to a decrease in the expectation value of the electron-nuclear attraction energy, an increase in the expectation value of the interelectronic repulsion energy, and an increase in the internuclear repulsion energy. These observations are consistent with a contraction of the electron cloud. The dominant factor in the −0.0550 hartree Jahn–Teller distortion (Td→C2v) in CH+4 is the −0.5262 hartree change in the electron–nuclear attraction energy. The differences in all energy components are large in relation to the JT distortion. Interelectronic repulsion plays a dominant role in determining the relative energies of the possible JT distorted structures, but electron correlation effects are relatively unimportant.