Spin current in the early stage of radical reactions and its mechanisms

Abstract

We study the electronic spin flux (atomic-scale flow of the spin density in molecules) by a perturbation analysis and ab initio nonadiabatic calculations. We derive a general perturbative expression of the charge and spin fluxes and identify the driving perturbation of the fluxes to be the time derivative of the electron-nucleus interaction term in the Hamiltonian. We then expand the expression in molecular orbitals so as to identify relevant components of the fluxes. Our perturbation theory describes the electronic fluxes in the early stage of reactions in an intuitively clear manner. The perturbation theory is then applied to an analysis of the spin flux obtained in ab initio calculations of the radical reaction of O2 and CH3· starting from three distinct spin configurations; (a) CH3· and triplet O2 with total spin of the system set Stot=1/2 (b) CH3· and singlet O2, Stot=1/2, and (c) CH3· and triplet O2, Stot=3/2. Further analysis of the time-dependent behaviors of the spin flux in these numerical simulations reveals (i) the spin flux induces rearrangement of the local spin structure, such as reduction of the spin polarization arising from the triplet O2 and (ii) the spin flux flows from O2 to CH3· in the reaction starting from spin configuration (a) and from CH3· to O2 in that starting from configuration (b), whereas no major intermolecular spin flux was observed in that starting from configuration (c). Our study thus establishes the mechanism of the spin flux that rearranges the local spin structures associated with chemical bonds.