On the Jahn-Teller and pseudo-Jahn-Teller effects in the photoelectron spectrum of cyclopropane

Abstract

We present a theoretical account of the Jahn-Teller (JT) and pseudo-Jahn-Teller (PJT) effects in the photoelectron spectrum of cyclopropane. The PJT interactions between the two JT split over(X, ̃)2 E′ and over(A, ̃)2 E″ electronic states of the cyclopropane radical cation are examined. Nuclear dynamical simulations on the resulting four coupled electronic states including fourteen relevant vibrational modes are carried out by a wave packet propagation approach employing the multiconfiguration time-dependent Hartree algorithm. The theoretical results are compared with recent experimental photoelectron spectroscopic data. © 2007 Elsevier B.V. All rights reserved.