Core-level positive-ion and negative-ion fragmentation of gaseous and condensed HCCl3 using synchrotron radiation.

We investigated the dissociation dynamics of positive-ion and negative-ion fragments of gaseous and condensed HCCl(3) following photoexcitation of Cl 2p electrons to various resonances. Based on ab initio calculations at levels HF/cc-pVTZ and QCISD/6-311G∗, the first doublet structures in Cl L-edge x-ray absorption spectrum of HCCl(3) are assigned to transitions from the Cl (2P(3/2),(1/2)) initial states to the 10a(1)(∗) orbitals. The Cl 2p → 10a(1)(∗) excitation of HCCl(3) induces a significant enhancement of the Cl(+) desorption yield in the condensed phase and a small increase in the HCCl(+) yield in the gaseous phase. Based on the resonant photoemission of condensed HCCl(3), excitations of Cl 2p electrons to valence orbitals decay predominantly via spectator Auger transitions. The kinetic energy distributions of Cl(+) ion via the Cl 2p → 10a(1)(∗) excitation are shifted to higher energy ∼0.2 eV and ∼0.1 eV relative to those via the Cl 2p → 10e(∗) excitation and Cl 2p → shape resonance excitation, respectively. The enhancement of the yields of ionic fragments at specific core-excited resonance states is assisted by a strongly repulsive surface that is directly related to the spectator electrons localized in the antibonding orbitals. The Cl(-) anion is significantly reinforced in the vicinity of Cl 2p ionization threshold of gaseous HCCl(3), mediated by photoelectron recapture through post-collision interaction.