Structural Origins of Electron Transfer Rates Across Self-Assembled Monolayers

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9412720 Chidsey This research project addresses the structural origins of the rates of long distance electron transfer across interfaces. It is supported by the Analytical and Surface Chemistry program, with a goal of understanding the role of intervening and surrounding material in the transfer of electrons between a metal electrode and a precisely positioned electroactive species. The continuum dielectric model will be examined as a basis for understanding and predicting the activation barrier to electron transfer, the role of electroactive species located between the metal and the polar electrolyte will be examined, and the effect of electronic states of the spacer material on electron transfer will be probed in these studies. Thiol monolayers on gold electrodes form the basis for these electron transfer studies. These measurements will have impact on the development of new sensor and display technologies, and will help to develop an understanding of interfacial charge transfer in applications ranging from biology to microelectronics. %%% In order to understand the rates and mechanisms of charge transfer between electrodes and electroactive species, a number of model approaches have been developed. One very promising approach uses self assembled monolayer technology to position the electroactive species and to control the structure and electronic properties of the medium through which electron transfer occurs. The work supported here uses this approach to examine the structural origins of the rates of charge transfer across interfaces. Knowledge in this area is crucial to understanding the mechanisms of biological membrane charge transfer, and in the development of new sensing and display technologies. The work supported here will contribute to the development of this understanding.