Features in the electronic absorption spectra of dithiocarboxylate functional groups, R-CS2-, are typically assigned based on well-studied thiocarbonyl compounds, C=S. Our preliminary findings, however, tells us how complex the molecular orbitals and electronic states are for dithiocarboxylates compared to thiocarbonyls. Some of the lowest electronic states of dithiocarboxylates consists of charge transfer character nπ*, π π*, and σ π*. Based on the lowest electronic states, dithiocarboxylates exhibit moderate substituent effect and an insensitive solvent effect. Density functional theory (DFT) calculations were employed to model the ground state structures and electronic states of dithiocarboxylates. All calculations utilized the PBE0 functional with D3 dispersion correction for structure optimizations and CAM-B3LYP functional for excitation energy computations. For structure optimizations, the def2-spvd basis set was used on all atoms, while time-dependent DFT (TDDFT) excitation energy computations employed def2-tzvpd. All calculations were calculated in different solvents using SMD/PCM model to account for solvent effects.

Theoretical investigation of the electronic properties on the dithiocarboxy functional group, R-CS2−

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ACS Spring 2020 National Meeting & Expo

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