Imaging of direct photodetachment and autodetachment of (OCS)2-: excited-state dynamics of the covalent dimer anion

We report a photoelectron imaging study of (OCS)-2 and compare the results to OCS-.H2O. Two electron-emission mechanisms are observed for the dimer anion: direct photodetachment and autodetachment, while OCS-.H2O exhibits only the direct mechanism. The results provide evidence of covalent (OCS)-2 coexisting with the OCS-.OCS cluster anion. The autodetachment originating from the covalent species is modeled as thermionic emission transpiring in the regime of fragmentation. The bulk statistical model is found applicable to the small anion due to the availability of low-lying excited states.