Abstract
The global descriptors of the chemical activity: ionization potential IP, electron affinity EA, chemical potential μ, absolute electronegativity χ, molecular hardness η and softness S, electrophilicity index ω, electro-donating ω(-), electro-accepting ω(+) powers as well as Ra and Rd indexes for gallic acid (GA) in the gas phase and water medium have been determined. To this aim, the HOMO and LUMO energies were calculated using the DFT method at the B3LYP, M06-2X, LC-ωPBE, BHandLYP, ωB97XD/cc-pVQZ theory levels using C-PCM, IEF-PCM and SMD solvation models, enabling more accurate descriptor calculations than those carried out so far. Quantum-chemical computations were also applied to investigate the GA structure and thermodynamic parameters characterizing its radical scavenging properties. To this aim, the full optimization of the neutral GA and its radical, cationic and anionic forms in vacuum and water medium has been performed, and then the bond dissociation enthalpy BDE, adiabatic ionization potential AIP, proton dissociation enthalpy PDE, proton affinity PA, electron transfer enthalpy ETE, gas phase acidity H(acidity) and free Gibbs acidity G(acidity) in water have been determined. The calculations revealed that GA in vacuum scavenges free radicals via hydrogen atom transfer (HAT), whereas in water (polar) medium by sequential proton loss electron transfer (SPLET). Analysis of the global activity descriptors of GA indicates that only B3LYP method combined with different solvation models satisfactory reproduces LUMO-HOMO energies and provides the smallest value of the total electron energy of GA. Among the parameters of chemical activity, the indexes Ra and Rd are the most independent of the computational method and the solvation model used. They can be recommended as a reliable source of information on the antioxidant activity of chemical compounds.