Keywords

CS2 molecular ion, molecular properties, CS+2, collisionally activated dissociation, RRKM, unimolecular decay rate

Abstract

Several common elementary methods of computing molecular properties, prerequisite to molecular dynamics studies, are tested for their validity for CS+2. Judged sufficiently accurate, these methods are then used to aid in investigating the collisionally activated dissociation of CS+2 upon impact with xenon. Rice–Ramsperger–Kassel–Marcus (RRKM) unimolecular decay rate calculations are presented and compared to experimental studies employing collisional activation. RRKM theory is shown to reproduce the experimental results for collision energies near threshold. When corrected for vibrational anharmonicity, the RRKM calculation shows agreement with the experimental results over a slightly wider range of energies. A discussion is given on the applicability of the "adiabatic criteria'' to describing electronic excitations in the collisional activation process. This model is shown to provide a better description of the activation process than direct vertical excitation.

Original Publication Citation

Sohlberg, Karl and Yibai Chen."The structure and dynamics of the CS[sub 2] molecular ion." The Journal of Chemical Physics 11 (1994): 3831-3839.