Theoretical Interpretation of the UV−vis Spectrum of the CS₂/Cl Complex in the Spectral Region 320−550 nm

Abstract

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 ClSCS, 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.

Spectroscopic Investigation of Chalcogen Bonding: Halide–Carbon Disulfide Complexes

“…These three structural forms are all loosely‐bound intermolecular complexes, however, the halogen radical can also form a covalent bond with the carbon atom and thus form a molecular radical rather than an intermolecular complex (Figure 3D). The neutral dimer complexes formed between a CS 2 molecule and a chlorine radical have previously been investigated both experimentally and computationally [40–43] . Previous computational studies located two of the four geometries reported in this study, with the bifurcated and linear geometries ( i. e .…”

“…The neutral dimer complexes formed between a CS 2 molecule and a chlorine radical have previously been investigated both experimentally and computationally. [40][41][42][43] Previous computational studies located two of the four geometries reported in this study, with the bifurcated and linear geometries (i. e. Figure 3B and 3C) having not been previously optimised.…”

Conformations and Vibrational Frequencies of a Precursor of Benzovesamicol Analogues Studied by Density Functional Theories

“…[10][11][12][13][14][15][16] Approximations in DFT permit the accurate calculation of certain physical quantities. The most widely used approximation in physics is the local-density approximation (LDA).…”