A SEQUENTIAL FORMULA FOR ELECTRONIC COUPLING IN LONG-RANGE BRIDGE-ASSISTED ELECTRON-TRANSFER - FORMULATION OF THEORY AND APPLICATION TO ALKANETHIOL MONOLAYERS

A recursion relation is formulated for the Green's function for calcul ating the effective electron coupling in bridge-assisted electronic tr ansfer systems, within the framework of the tight-binding Hamiltonian. The recursion expression relates the Green's function of a chain brid ge to that of the bridge that is one unit less. It is applicable regar dless of the number of orbitals per unit. This method is applied to th e system of a ferrocenylcarboxy-terminated alkanethiol on the Au(111) surface. At larger numbers of bridge units, the effective coupling str ength shows an exponential decay as the number of methylene(-CH2-) uni ts increases. This sequential formalism shows numerical stability even for a very lung chain bridge and, since it uses only small matrices, requires much less computer time for the calculation. Identical bridge units are not a requirement, and so the method can be applied to more complicated systems. (C) 1997 American Institute of Physics.