Vibronic dynamics in the low-lying coupled electronic states of methyl cyanide radical cation

Abstract

Static and dynamic aspects of the Jahn–Teller (JT) and pseudo-Jahn–Teller (PJT) interactions between the ground and first excited electronic states of the methyl cyanide radical cation are theoretically investigated here. The latter involves construction of a theoretical model by ab initio computation of electronic potential energy surfaces and their coupling surfaces and simulation of the nuclear dynamics employing time-independent and time-dependent quantum mechanical methods. The present system represents yet another example belonging to the (E + A ) ⊗ e JT–PJT family, with common JT and PJT active degenerate (e) vibrational modes. The theoretical results are found to be in very good accord with the recent experimental data revealing that the JT interactions are particularly weak in the ground X^~2E electronic manifold of methyl cyanide radical cation, On the other hand, the PJT interactions of this ground electronic manifold with the first excited A^∼2A₁ electronic state of the radical cation are stronger which cause an increase of the spectral line density. The effect of deuteration on the JT–PJT dynamics of the methyl cyanide radical cation is also discussed.