HSO3Cl: a prototype molecule for studying OH-stretching overtone induced photodissociationElectronic supplementary information (ESI) available. See DOI: 10.1039/c5cp07319g

Vibrationally induced photodissociation in sulfurochloridic acid (HSO 3 Cl) is found to be a viable process to form SO 3 and HCl from excitations of the OH-stretching overtone starting at ν OH = 4. Reactive molecular dynamics simulations on a fully-dimensional potential energy surface fitted to MP2 calculations show that hydrogen transfer and HCl elimination compete with one another on the nanosecond time scale. Excitation with 5 and 6 quanta in the OH-stretch direct elimination of HCl is a dominant process on the several hundred picosecond time scale. At longer times, HCl formation is preceded by intramolecular hydrogen transfer and concomitant excitation of torsional degrees of freedom. As HSO 3 Cl is a suitable proxy for H 2 SO 4 , which is relevant for weather and climate in the upper atmosphere, it is concluded that vibrationally induced photodissociation is a possible mechanism for H 2 SO 4 decomposition. Final state energy distributions for different internal degrees of freedom are predicted which should be observable in laboratory measurements. Vibrationally induced photodissociation in sulfurochloridic acid (HSO 3 Cl) is found to be a viable process to form SO 3 and HCl from excitations of the OH-stretching overtone starting at ν OH = 4.