Sub-nanosecond secondary geminate recombination in mercury halides HgX2 (X = I, Br) investigated by time-resolved x-ray scattering

In this work, we present a detailed investigation on the recombination dynamics of mercury halides HgX2 (X = I, Br) in acetonitrile solution after UV-induced photodissociation. The study is performed by combining time-resolved wide-angle x-ray scattering (TRWAXS) and optical transient absorption spectroscopy. Up to 68% of the UV (266 nm) photodissociated HgX and X radicals that escape the solvent cage surrounding parent HgX2 recombine within a nanosecond after photodissociation. In contrast to classical primary geminate recombination, occurring on much faster time scales, we interpret the sub-nanosecond recombination channel as secondary geminate recombination (SGR), also referred to as diffusion-limited geminate recombination. The family of triatomic mercury halides therefore represents an important class of molecules to study chemical mechanisms of solvent-dependent SGR by TRWAXS. The methodology described here allows for direct mapping of the time-dependent inter-radical distance distribution function, a critical parameter for the assessment of the SGR dynamics in solution phase and solvation in general. Published under license by AIP Publishing.