Photodissociation Dynamics of H _\textbf2 S ^\textbf+ near 325 nm

We study the photodissociation dynamics of the hydrogen sulfide cations (H _2 S ^+ ) using the time-sliced velocity map ion imaging (VMI) technique and high-accuracy calculations. High-resolution ion images of the S ^+ ( ^4 S) products were measured at four photolysis wavelengths of 325.158, 325.200, 325.243, 325.307 nm, which correspond to the excitation to the A ^2 A _1 (0, 13, 0) K =1 state of H _2 S ^+ . Rotational state-resolved total kinetic energy releases and angular distributions have been derived as a function of the photolysis wavelengths. Notably, photolysis wavelength dependent product rotational state and anisotropy parameter distributions have been clearly observed. Full-dimensional potential energy surface characterization suggests that nonadiabatic coupling between A ^2 A _1 and B ^2 B _2 states at C_2 \textv configurations, as well as relaxation of the symmetry to C_ \texts in the conical intersection region between the two states, plays a key role in the photodissociation process.