ABSTRACT This study investigates the structural and stability characteristics of diaryl dichalcogenide radical anions using quantum chemical methods. Density functional theory (DFT) calculations are performed with B3LYP, B3LYP‐D, B3LYP‐D3, B3LYP‐D3BJ, LC‐ωHPBE, MN15, M06HF, M08‐HX, ωB97XD, and B2PLYP functionals to determine structural and energetic features of (R─Ch─Ch─R) neutral and radical anion species in aqueous medium. Here, R refers to Ph, o‐CH 3 ‐Ph, o‐OH‐Ph, o‐NO 2 ‐Ph, m‐NH 2 ‐Ph, p‐NH 2 ‐Ph, m‐Cl‐Ph, p‐Cl‐Ph, and PhCH 2 groups, while Ch corresponds to S, Se, or Te atoms. Benchmark calculations are supported by MP2 and CCSD(T) methods, alongside solvation effects modeled through the SMD continuum approach. Def2‐TZVPP basis sets enhance accuracy for tellurium systems, while LANL2DZ is tested for computational efficiency. Structural benchmarking against crystallographic data confirms that B3LYP and dispersion‐corrected variants, along with LC‐ωHPBE and M06HF, provide reliable geometrical descriptions. Energetics predicted with B2PLYP, B3LYP‐D3BJ, ωB97XD, and M08‐HX align closely with CCSD(T). Results reveal that Def2‐TZVPP consistently outperforms LANL2DZ and 6–311++G(d,p). High stability is observed for the (o‐OH‐Ph‐Se) 2 •− radical anion, attributed to reduced π–π* stacking interactions. Radical anions display two‐center three‐electron (2c─3e) bonds between chalcogen atoms, giving rise to visible‐region absorption through σ → σ * transitions. Comparisons highlight the important electronic features of Te‐based systems relative to sulfur and selenium analogues with biomedical relevance.
Kumar et al. (Sun,) studied this question.