The electronic matrix element responsible for electron exchange in a series of metal dimers was calculated using ab initio wave functions. The distance dependence is approximately exponential for a large range of internuclear separations. A localized description, where the two nonorthogonal structures characterizing the electron localized at the left and right sites are each obtained self‐consistently, is found to provide the best description of the electron exchange process. We find that Gaussian basis sets are capable of predicting the expected exponential decay of the electronic interactions even at quite large internuclear distances.
© 1987 American Institute of Physics
Theoretical studies of electron transfer in metal dimers: XY+→X+Y, where X, Y=Be, Mg, Ca, Zn, Cd. Robert J. Cave, David V. Baxter, William A. Goddard III, and John D. Baldeschwieler, J. Chem. Phys. 87, 926 (1987), DOI: 10.1063/1.453247