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 H(2)S, derived from cutting-edge translational spectroscopy measurements of the H, S((1)D) and S((1)S) 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(X), SH(A) and H(2) co-fragments, and the atomisation routes leading to two H atoms along with S((3)P) and S((1)D) 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 (1)A' and (1)A'' symmetry. The comprehensive picture of the wavelength-dependent (or vibronic state-dependent) photofragmentation behaviour of H(2)S 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.