The hydrogen bond strength, molecular geometry, π-electron delocalization, and physical properties such as dipole moment, chemical potential, and chemical hardness of 4-nitropyridine-3-thiol and its 29 derivatives have been studied by means of density functional method with 6-311++G** basis set in gas phase and water solution. Also, the excited-state properties of intramolecular hydrogen bonding in these systems have been investigated theoretically using the time-dependent density functional theory method. The HOMA, NICS, PDI, ATI, FLU, and FLUπ indices as well-established aromaticity indicators have been examined. Natural bond orbital analysis is also performed for better understanding the nature of intramolecular interactions. The electron density and Laplacian (∇2ρ) properties, estimated by AIM calculations, indicate that H···O bond possesses low ρ and positive ∇2ρ values, which are in agreement with electrostatic character of the HBs, whereas S–H bond has covalent character. Numerous correlations between topological, geometrical, and energetic parameters are also found.
