Napper, Andrew Michael
(2003)
Electron Transfer through Thin Organic Films and Highly Curved Donor-Bridge-Acceptor Molecules.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
Abstract
Electron-transfer rate constants were measured for a variety of molecular systems. Therate constant was found to depend upon the nature of the medium between the electron donor andacceptor moieties. Using a superexchange model to calculate the electronic coupling betweendonor and acceptor, the effect of orbital energetics was studied. For photoinduced electrontransfer, aromatic moieties with large electron affinities promote large electronic couplingmagnitudes. In the electrochemical systems studied involving a gold electrode and animmobilized ferrocene tethered alkanethiol, alkane chains were found to be more efficient atpromoting electron transfer than chains incorporating ether linkages. This indicates a dominanthole-transfer mechanism for the electrochemical systems. Chemical modification of adjacentdiluent alkanethiols also resulted in alteration of the rate constant. This suggests intermolecularinteractions are important in electron transfer in these systems.
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Details
| Item Type: |
University of Pittsburgh ETD
|
| Status: |
Unpublished |
| Creators/Authors: |
| Creators | Email | Pitt Username | ORCID  |
|---|
| Napper, Andrew Michael | napper@pitt.edu | NAPPER | |
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| ETD Committee: |
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| Date: |
10 March 2003 |
| Date Type: |
Completion |
| Defense Date: |
30 August 2002 |
| Approval Date: |
10 March 2003 |
| Submission Date: |
5 September 2002 |
| Access Restriction: |
No restriction; Release the ETD for access worldwide immediately. |
| Institution: |
University of Pittsburgh |
| Schools and Programs: |
Dietrich School of Arts and Sciences > Chemistry |
| Degree: |
PhD - Doctor of Philosophy |
| Thesis Type: |
Doctoral Dissertation |
| Refereed: |
Yes |
| Uncontrolled Keywords: |
C-Clamp; DBA; electrochemistry; electron transfer; photoinduced |
| Other ID: |
http://etd.library.pitt.edu:80/ETD/available/etd-09052002-115124/, etd-09052002-115124 |
| Date Deposited: |
10 Nov 2011 20:01 |
| Last Modified: |
15 Nov 2016 13:50 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/9329 |
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