PHYS 33 |
| Electron transfer (ET) is fundamental to most chemical, electrochemical, and photochemical energy harvesting and storing processes. Marcus theory enjoys widespread success in understanding ET from a microscopic perspective. Only in the last decade have computational methodologies and hardware advanced enough to allow ab initio treatments of ET in many molecules of interest. Even so, a number of key influences are often neglected in such treatments. In an effort to map the relative importance of such influences, we have analyzed the impact of solvent fields through polarizable continuum methods, zero point energies, and photoexcitation on electron transfer in a series of experimentally well-characterized organic donor and acceptor molecules. An integrated picture of electrochemical and photo-induced electron transfer is emerging. Continuum solvation strongly modifies electron affinities and ionization energies, whereas the reorganization energies are much less affected. Zero point energy differences are found to be non-negligible, though it is unlikely they will alter the relative reactivities of most couples. |
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Computational Electrochemistry for New Energy
8:20 AM-12:00 PM, Sunday, August 19, 2007 BCEC -- 160A, Oral
Division of Physical Chemistry |