The vibronic state dependent predissociation of H₂S: determination of all fragmentation processes

Abstract

Photochemistry plays a significant role in shaping the chemical reaction network in the solar nebula and interstellar clouds. However, even in a simple triatomic molecule photodissociation, determination of all fragmentation processes is yet to be achieved. In this work, we present a comprehensive study of the photochemistry of H₂S, derived from cutting-edge translational spectroscopy measurements of the H, S(¹D) and S(¹S) atom products formed by photolysis at wavelengths across the range 155-120 nm. The results provide detailed insights into the energy disposal in the SH(<i>X</i>), SH(<i>A</i>) and H₂ co-fragments, and the atomisation routes leading to two H atoms along with S(³P) and S(¹D) atoms. Theoretical calculations allow the dynamics of all fragmentation processes, especially the bimodal internal energy distributions in the diatomic products, to be rationalised in terms of non-adiabatic transitions between potential energy surfaces of both ¹A' and ¹A'' symmetry. The comprehensive picture of the wavelength-dependent (or vibronic state-dependent) photofragmentation behaviour of H₂S will serve as a text-book example illustrating the importance of non-Born-Oppenheimer effects in molecular photochemistry, and the findings should be incorporated in future astrochemical modelling.