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SOLVENT MEDIATED ELECTRON TRANSFER IN C-CLAMP SHAPED MOLECULES

Read, Ian Anthony (2009) SOLVENT MEDIATED ELECTRON TRANSFER IN C-CLAMP SHAPED MOLECULES. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Abstract

The role of solvent in mediating the electronic coupling between an electron donor and acceptor is investigated. The temperature dependent electron transfer rate constants in two C-clamp shaped Donor-Bridge-Acceptor (DBA) molecules are used to evaluate the electronic coupling between the donor and acceptor sites. By varying the solvent, it is demonstrated that the donor-acceptor electronic couping is strongly dependent on both the electronic nature and the position of the intervening medium. An experimental strategy that utilizes the semiclassical treatment of electron transfer together with a molecular based solvation model is introduced and shown to be a reliable way of determining the magnitude of the electronic coupling. The results demonstrate a strong dependence of the electronic coupling on the relative energy between the donor excited state energy and the intervening structure's LUMO energy. An observation consistent with electron mediated 'superexchange.' In addition, the dependence of the electron transfer rate on solvent position is evaluated. These results are consistent with a temperature dependent electronic coupling mechanism.

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Details

Item Type: University of Pittsburgh ETD
Status: Unpublished
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Read, Ian Anthonyiar8@pitt.eduIAR8
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairWaldeck, David Hdave@pitt.eduDAVE
Committee MemberPratt, David Wpratt@pitt.eduPRATT
Committee MemberKurnikova, Mariakurnikova@cmu.edu
Committee MemberSaxena, Sunilsksaxena@pitt.eduSKSAXENA
Date: 22 June 2009
Date Type: Completion
Defense Date: 17 February 2009
Approval Date: 22 June 2009
Submission Date: 1 April 2009
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: donor-bridge-acceptor; semiclassical; superexchange
Other ID: http://etd.library.pitt.edu/ETD/available/etd-04012009-013708/, etd-04012009-013708
Date Deposited: 10 Nov 2011 19:33
Last Modified: 15 Nov 2016 13:38
URI: http://d-scholarship.pitt.edu/id/eprint/6684

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