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Columbia Dissertations and Theses > Doctoral Dissertations
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| Author(s): | Crystal, Joseph |
| Title: | Ab initio quantum chemical calculations of the kenetics and energetics of electron transfer reactions |
| Physical Description: | vi, 95 leaves, bound. |
| Issue Date: | 2001 |
| Description: | Department: Chemistry. Thesis (Ph. D.)--Columbia University, 2001. |
| Bookmark as: | http://hdl.handle.net/10022/AC:P:4642 |
| Full Text (ProQuest): | /ac/proxit.jsp?url=http://gateway.proquest.com/ope... |
| Abstract: | Ab initio quantum chemical techniques are used to calculate the rate of electron transfer in two systems: ferrocene-ferrocenium and the Scanning Tunneling Microscope (STM). The ferrocene-ferrocenium system is used to test the accuracy of the ab initio results with previously obtained theoretical and experimental results. The results are in good qualitative agreement and the discrepancies are noted and explained. The same ab initio techniques are modified and utilized to reproduce the image contrasts obtained with the STM for functionalized alkanes physisorbed on graphite. The results are in good accord with experimental results. The theoretical model is shown to be able to distinguish between different conformations of molecules physisorbed on the graphite surface. The results illustrate the dependence of the STM image contrasts on both the geometry and electronic structure of the adsorbate molecules. The energetics of the electron transfer process in the photosynthetic reaction center are then studied using density functional theory. In particular, the ionization energies and electron affinities for the porphyrin rings involved in the electron transfer process are calculated. With the use of a Poisson-Boltzmann solver, the redox potentials are then calculated. The results show a significant improvement relative to previously obtained results at the Hartree-Fock level. An outline of future work concludes the discussion of the photosynthetic reaction center. |
| Collection(s): | Doctoral Dissertations |
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