Fragmentation dynamics of CH 3 Cl q + ( q = 2,3): theory and experiment.

A combined theoretical and experimental study of the dissociation of the di- and trication of the CH 3 Cl molecule has been performed. Experimentally, these multi-charged ions were produced after interactions of a CH 3 Cl effusive jet with a mono-energetic beam of H + or Ar 9+ projectile ions. Theoretically, we mapped the multi-dimensional potential energy surfaces of CH 3 Cl 2+ , H 2 CClH 2+ and CH 3 Cl 3+ species in their electronic ground and electronically excited states using post-Hartree-Fock configuration interaction methods. In addition to the obvious bond-breaking ionic fragments ( i.e. H + + CH 2 Cl + , H + + CH 2 Cl 2+ and CH 3 + + Cl + ), the formation of H 2 + (+CHCl + or CHCl 2+ ), H 3 + (+CCl + ) and HCl + (+CH 2 + ) was observed upon bond rearrangement after ion impact of CH 3 Cl. The interaction strength of the incident projectiles is found to affect the relative yields on the observed dissociation channels, however, it has no effect on the kinetic energy releases of the fragmentation pathways. For the observed dissociation channels, plausible formation mechanisms were proposed. These reaction pathways take place on the ground and/or electronic excited potential energy surfaces of the doubly and triply charged CH 3 Cl ions, where spin-orbit and vibronic couplings are in action. Moreover, this work suggests that the mechanisms undertaken may depend on the multiply charged ion preparation by valence or inner-shell single photon photoionization, fast ion beam impact or ultrafast intense laser ionization.