This work presents a density functional theory study of Ofloxacin (OFL) as a medicine with antibiotic activity. The Conformational behaviour, gas-phase acidity and metal ion affinity (MIA) analysis of the Ofloxacin with some selected cations from alkali (Li+, Na+, and K+), alkaline-earth (Be2+, Ca2+ and Mg2+) and transition (Zn2+, Cu2+, Ni2+, Co2+ and Fe2+) metals were explored. All structural optimizations were performed at the M06–2X level of theory with 6-311++G(d,p) using the basis set. The calculations demonstrated the following MIA order: OFL-Be2+ > OFL-Ni2+ > OFL-Co2+ > OFL-Cu2+ > OFL-Fe2+ > OFL-Zn2+ > OFL-Mg2+ > OFL-Ca2+ > OFL-Li+ > OFL-Na+ > OFL-K+. The results also showed that the MIA values are decrease in aqueous solution because of solvation effects. Natural bond orbital theory (NBO) and quantum theory of atoms in molecules (QTAIM) were used to probe the charge transfer process and the nature of interactions in the formed complexes. The results of the NBO analysis revealed that the charge transfer occurs from OFL and Mn+ with the metal cations acting as charge acceptors and the amount of charge transfer is in agreement with MIA. The QTAIM analysis shows that the (M–O) coordination interactions are quasi-covalent in complexes formed between OFL and alkali or alkaline-earth metal cations, whereas they are covalent in complexes formed with the transition metal cations and Be2+. The results confirm that the strengths of the interactions are in good agreement with electron densities at the bond critical points (BCP).
