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

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 (X) over bar E-2' and (A) over bar E-2 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. (c) 2007 Elsevier B.V. All rights reserved.