Theoretical interpretation of the UV-vis spectrum of the CS2/Cl complex in the spectral region 320-550 nm.

Accurate multireference configuration interaction and time-dependent density functional calculations have been performed to interpret the experimental UV-vis spectrum of the CS 2 /Cl complex in the spectral region 320-550 nm. The molecular structure of the complex responsible for the previously observed UV-vis spectrum is recognized as CISCS, not ClCS 2 . Two low-lying excited states of ClSCS, responsible for its optical absorption, have been identified and analyzed. Optical excitation of ClSCS leads to the excitation-specific bond elongation that may lead to photofragmentation of the molecule. In addition, experimental conditions for verifying the presence of ClCS 2 are identified and detailed characterization of its optically active excited states with possible photofragmentation pathways is given.