The Jahn-Teller effect in the triply degenerate electronic state of methane radical cation

作者：Mondal T; Varandas A J C^*

来源：Journal of Chemical Physics, 2011, 135(17): 174304.

DOI：10.1063/1.3658641

• ab initio calculations
• ground states
• Jahn-Teller effect
• molecular electronic states
• organic compounds
• photoelectron spectra
• vibronic states

A quantum dynamics study is performed to examine the complex nuclear motion underlying the first photoelectron band of methane. The broad and highly overlapping structures of the latter are found to originate from transitions to the ground electronic state, (X) over tilde T-2(2), of the methane radical cation. Ab initio calculations have also been carried out to establish the potential energy surfaces for the triply degenerate electronic manifold of CH4+. A suitable diabatic vibronic Hamiltonian has been devised and the nonadiabatic effects due to Jahn-Teller conical intersections on the vibronic dynamics investigated in detail. The theoretical results show fair accord with experiment.

• 出版日期2011-11-7