Bond analysis in meta- and para-substituted thiophenols: overlap descriptors, local mode analysis, and QTAIM.

Context: This study delves into the chemical nuances of thiophenols and their derivatives through a comprehensive computational analysis, moving beyond traditional energetic perspectives such as bond dissociation enthalpy and S-H dissociation dynamics. By employing the overlap model along with its topological descriptors (OP/TOP), quantum theory of atoms in molecules (QTAIM), and local vibrational mode (LVM) theories, the research provides a deeper understanding of the S-H and C-S bonding scenarios in substituted thiophenols. The investigation follows the electron-donating capacity of S-H substituent variation with the nature and positioning of other ring substituents.