Bryantsev V. Quantum chemical description of physicochemical characteristics of conjugated radicals and ion-radicals

The thesis is devoted to development and extension of reliable procedure for calculation of physicochemical characteristics of systems with open electronic shell. Quantum chemical calculations were carried out in terms of coupled p-electronic perturbation theory using unrestricted Hartree-Fock method. There have been revealed conformities of changing the enthalpies of formation, bond dissociation energies, ionization potentials, ESR coupling constants, bond lengths, electrical dipole polarizabilities, diamagnetic susceptibilities, induced p-electron ring currents and energies of the lowest electronic transitions on the structure of the conjugated radicals, radical ions and radical ion carbenes studied. Electrocyclization of the radicals of odd polyenes, radical ions of even polyenes, polyenes in the lowest triplet state and methylencyclopropane derivatives have been described in terms of the Fukuy index approach. Analysis of substituent effects on reaction rate constants with radical character of Transition State has been done. Quantum chemical model of adsorption of organic molecules and radicals on metal surface in solutions of electrolyte is proposed. The results of calculations are in agreement with available experiment.