Influence of Vibrational Resonances and Coriolis Coupling on Dissociation Rates in the Near-threshold Unimolecular Fragmentation of HOCl

Abstract

The unimolecular dissociation of HOCl in the ground electronic state near the HOϩCl fragmentation threshold is investigated employing an ab initio potential energy surface. The dynamics calculations are performed by using an imaginary absorbing potential and filter diagonalization. The computational study is mainly focused on the influence of accidental or systematic vibrational resonances on the total angular momentum dependence of dissociation rates and the importance of Coriolis interaction.

Renner–Teller induced predissociation of HNO(Ã 1A″): Rotational-state dependent linewidths of quasibound states

“…[45][46][47][48] Monitoring the decay width for vibrational state ͑6,0,0͒ ͑v 1 is the HO vibrational quantum number͒ as a function of J shows several fluctuations, which qualitatively can be explained in an analogous way as described for the HNO predissociation. [45][46][47][48] Monitoring the decay width for vibrational state ͑6,0,0͒ ͑v 1 is the HO vibrational quantum number͒ as a function of J shows several fluctuations, which qualitatively can be explained in an analogous way as described for the HNO predissociation.…”

The unimolecular dissociation of HCO. V. Mixings between resonance states

“…Another recent example for mixing between resonance states with profound influence on the dissociation rate is the dissociation of HOCl in its ground electronic state. [7][8][9][10]23 Like HNO, the interaction is tuned by variation of the total angular momentum quantum number J.…”

State-to-state unimolecular reaction dynamics of highly vibrationally excited molecules

“…The experimental and theoretical investigation of HOCl unimolecular dynamics have synergistically driven each other during the past few years, with the groups of Bowman 36,37 and of Schinke 35,38 tackling the latter with high quality ab initio calculations of the potential energy surface and dissociation dynamics. The complementarity of these calculations to experimental measurements stems from the former having access to a much larger amount of information, typically limited only by computational power.…”