eprintid: 6684
rev_number: 4
userid: 6
dir: disk0/00/00/66/84
datestamp: 2011-11-10 19:33:38
lastmod: 2016-11-15 13:38:04
status_changed: 2011-11-10 19:33:38
type: thesis_degree
metadata_visibility: show
contact_email: iar8@pitt.edu
item_issues_count: 0
eprint_status: archive
creators_name: Read, Ian Anthony
creators_email: iar8@pitt.edu
creators_id: IAR8
title: SOLVENT MEDIATED ELECTRON TRANSFER IN C-CLAMP SHAPED MOLECULES
ispublished: unpub
divisions: sch_as_chemistry
full_text_status: public
keywords: donor-bridge-acceptor; semiclassical; superexchange
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.
date: 2009-06-22
date_type: completed
institution: University of Pittsburgh
refereed: TRUE
etdcommittee_type: committee_chair
etdcommittee_type: committee_member
etdcommittee_type: committee_member
etdcommittee_type: committee_member
etdcommittee_name: Waldeck, David H
etdcommittee_name: Pratt, David W
etdcommittee_name: Kurnikova, Maria
etdcommittee_name: Saxena, Sunil
etdcommittee_email: dave@pitt.edu
etdcommittee_email: pratt@pitt.edu
etdcommittee_email: kurnikova@cmu.edu
etdcommittee_email: sksaxena@pitt.edu
etdcommittee_id: DAVE
etdcommittee_id: PRATT
etdcommittee_id: 
etdcommittee_id: SKSAXENA
etd_defense_date: 2009-02-17
etd_approval_date: 2009-06-22
etd_submission_date: 2009-04-01
etd_access_restriction: immediate
etd_patent_pending: FALSE
assigned_doi: doi:10.5195/pitt.etd.2011.6684
thesis_type: dissertation
degree: PhD
committee: David H. Waldeck (dave@pitt.edu) - Committee Chair
committee: David W. Pratt (pratt@pitt.edu) - Committee Member
committee: Maria Kurnikova (kurnikova@cmu.edu) - Committee Member
committee: Sunil Saxena (sksaxena@pitt.edu) - Committee Member
etdurn: etd-04012009-013708
other_id: http://etd.library.pitt.edu/ETD/available/etd-04012009-013708/
other_id: etd-04012009-013708
citation:   Read, Ian Anthony  (2009) SOLVENT MEDIATED ELECTRON TRANSFER IN C-CLAMP SHAPED MOLECULES.  Doctoral Dissertation, University of Pittsburgh.    (Unpublished)  
document_url: http://d-scholarship-dev.library.pitt.edu/6684/1/ReadPhD021720092.pdf