화학공학소재연구정보센터
Journal of Chemical Physics, Vol.111, No.4, 1569-1579, 1999
Perturbation theory approach to tunneling: Direct and resonance transmission in super-exchange models
In this paper we examine, within simple models, different approaches to computing tunneling probabilities in super-exchange models of electron transfer. The relationship between tunneling calculations that use scattering theory type formalisms and approaches based on standing waves, which are more closely related to electron transfer between bound donor and acceptor states, is established. Transmission probabilities computed by using truncated basis representations are compared to exact analytical or numerical results for one- and two-dimensional models. We find that while resonance tunneling is well approximated by truncated basis approaches, computing deep tunneling using such basis sets can lead to large errors. Implications for calculations of bridge assisted electron transfer are discussed.