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Center for Nonlinear Studies |
The concept of a nuclear reaction coordinate plays a central and ubiquitous role in chemical reaction dynamics; however, for electron and energy transfer events, a well-defined reactions coordinates remains elusive. In a general sense, one defines a collective coordinate connecting the initial and final states of the system and we describe the influence of the environment in terms of the reorganization energy. We recently developed a novel search algorithm that is capable of extracting optimal electron and energy transfer paths between diabatic states. The algorithm, which is similar to the core method used by internet search engines such as Google and Netflix, determines a ranked set of collective nuclear modes that extremizes the electron-nuclear coupling terms from a given set of parameters determined from ab initio theory. The method is benchmarked against experimental results of Closs and Marcus theory with outstanding agreement in most cases. I will then discuss a recent application of the approach to examine competing electronic relaxation pathways in a platinum bridged Donor-bridge-acceptor complex recently studied by Weinstein’s group.
Host: Andrei Piryatinski