Excitation and Circular Dichroism Spectra of (+)-(S,S)-bis(2-Methylbutyl)chalcogenides

Abstract: Theoretical electronic spectra and natural circular dichroism (CD) spectra of (+)-(S,S)-bis(2-methylbutyl)chalcogenides, Ch[CH₂CH(CH₃)C₂H₅]₂ (Ch = S, Se, and Te), were calculated by the symmetry adapted cluster (SAC) and SAC-configuration interaction (SAC-CI) methods. Whereas the calculated CD spectrum for each stable conformation itself did not reproduce the corresponding experimental one, their Boltzmann-averaged spectra showed good agreement with the experimental results. We provided the assignment for each spectral band according to our calculation results. For the telluride compound, temperature dependence of the CD spectra was experimentally observed due to variation in the Boltzmann factor, and our calculations reproduced it qualitatively. The spectral features that we could not reproduce can be attributed to triplet transitions through the spin-orbit interaction effects as well as accuracy incompleteness on the calculation conditions.