Dissociation dynamics of simple chlorine containing molecules upon resonant Cl K-σ* excitation.

Abstract

A theoretical analysis of dissociation dynamics of chlorine K-σ(*) core-excited molecules is performed. The potential energy surfaces of HCl, Cl2, CH3Cl, CH2Cl2, CHCl3, CCl4, CFCl3, CF2Cl2, and CF3Cl are calculated along the normal vibrational modes of the ground electronic state yielding the widths of the corresponding Franck-Condon distributions. An insight into the potential energy surface of 1st σ(*) resonances shows that the initial dissociation dynamics of chloro(fluoro)methanes mainly involves the distancing of the carbon and the core-excited chlorine atom and is practically independent of other atoms in the molecule, which is in agreement with the recent experimental findings. The carbon atom pulls out the remaining three atoms shortly after piercing the three-atom plane resulting in a high vibrationally excited state of the fragment if the reconnection time is smaller than the lifetime of the L shell.