Theory of Electron Transfer and Related Reactions
Abstract
Publicly Releasable Abstract for ONR proposal on “Theory of Electron Transfer and Related Reactions” by Prof. Rudolph A. Marcus, California Institute of Technology for 1/1/16-12/31/18 In the proposed research it is planned to treat theoretically (1) the recombination of electrons and holes in a perovskite, in particular their ultrafast bimolecular recombination at room temperature and its observed decrease with increasing light intensity. To this end the effect of a Debye shielding of the charged carriers and its dependence on light intensity will be introduced. (2) It is planned to treat theoretically the complex-valued conductivity spectrum of semiconductors and in particular to understand and generalize the widely used Drude-Smith equation for that complex conductivity, a formalism for disordered systems that incorporates a back scattering of the charged carriers. It is planned to use a memory function formalism commonly used for the equivalent of back scattering in liquids, with the intention of understanding in a more fundamental way the Drude-Smith equation, as well as exploring its potential generalization. The results will be applied to experiments on time-resolved terahertz spectroscopy of photoexcited semiconductors. (3) It is planned to study the photoexcited injection of protons into layered solids and treat the recombination of charges, in particular, in the photo excitation of violamine and resultant injection of protons into potassium acid phthalate, a layered structure. The theory will be used to explain the intermittent fluorescence of the violamine that has a power law slope of roughly -1, both for the fluorescence on and the fluorescence off states. It is planned for this purpose to adapt a theory we developed for the photoinjection of an electron from a dye into Al2O3, a different kind of surface problem. (4) It is planned to formulate a theory for single molecule experiments on the controlled rotation of a molecular motor F1 ATPase, extending to this problem our recently published work on the theory of stalling experiments for the same mechano-chemical system. The detailed kinetics of steps such as the binding and release of the ATP and ADP and the phosphate ion release, with rate constants that are rotor angle-dependent will be treated, the rotor angle now changing at a constant rate in the controlled rotation. The research performed thus far during the current grant period (1/1/13-12/31/15) is also described in this proposal and includes (1) theory of pooling of infrared quanta by adsorbates on surfaces, (2) theory of intermittently fluorescing semiconductor nanoparticles and the role of Auger processes, (3) absorption and conductivity of perovskites, (4) theory of sum frequency generation of spectroscopy of dangling OH bonds at a water surface, (5) theory of rates, equilibrium constants and Brønsted slopes in F1-ATPase single molecule stalling experiments, and (6) miscellaneous topics. This abstract is publicly releasable.
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Jun 03, 2016
- Source ID
- N000141612203
Entities
People
- Rudolph A. Marcus
Organizations
- California Institute of Technology
- Office of Naval Research
- United States Navy