Rotational and nuclear-spin level dependent photodissociation dynamics of H(2)S

The detailed features of molecular photochemistry are key to understanding chemical processes enabled by non-adiabatic transitions between potential energy surfaces. But even in a small molecule like hydrogen sulphide (H(2)S), the influence of non-adiabatic transitions is not yet well understood. Here we report high resolution translational spectroscopy measurements of the H and S((1)D) photoproducts formed following excitation of H(2)S to selected quantum levels of a Rydberg state with (1)B(1) electronic symmetry at wavelengths λ ~ 139.1 nm, revealing rich photofragmentation dynamics. Analysis reveals formation of SH(X), SH(A), S((3)P) and H(2) co-fragments, and in the diatomic products, inverted internal state population distributions. These nuclear dynamics are rationalised in terms of vibronic and rotational dependent predissociations, with relative probabilities depending on the parent quantum level. The study suggests likely formation routes for the S atoms attributed to solar photolysis of H(2)S in the coma of comets like C/1995 O1 and C/2014 Q2.