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Electron Transfer through Thin Organic Films and Highly Curved Donor-Bridge-Acceptor Molecules.

Napper, Andrew Michael (2003) Electron Transfer through Thin Organic Films and Highly Curved Donor-Bridge-Acceptor Molecules. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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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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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Napper, Andrew Michaelnapper@pitt.eduNAPPER
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairWaldeck, David Hdave@pitt.eduDAVE
Committee MemberWalker, Gilbert Cgilbertw@pitt.eduGILBERTW
Committee MemberJordan, Kenneth Djordan@pitt.eduJORDAN
Committee MemberZimmt, Matthew
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:, etd-09052002-115124
Date Deposited: 10 Nov 2011 20:01
Last Modified: 15 Nov 2016 13:50


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