CORRELATION FORMULA FOR THE COUPLINGS AT CROSSINGS BETWEEN IONIC AND COVALENT MOLECULAR-STATES

From an analysis of empirical and theoretical information on ionic and covalent interactions, a relationship is established between the coup ling matrix elements (which measure the nonadiabatic splitting at avoi ded crossings and strongly influence transition probabilities) and bas ic quantities of separated partners (ionization potentials, electron a ffinities, polarizabilities). Although the systems considered here are limited to alkali atoms interacting with simple atoms and molecules, the proposed correlation rule paves the way for extensions to deal wit h electron transfer reaction dynamics for more general donor-acceptor couples. (C) 1997 American Institute of Physics.