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 X^˜2E′ and A^˜2E″ 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.