eprintid: 9329
rev_number: 4
userid: 6
dir: disk0/00/00/93/29
datestamp: 2011-11-10 20:01:48
lastmod: 2016-11-15 13:50:06
status_changed: 2011-11-10 20:01:48
type: thesis_degree
metadata_visibility: show
contact_email: napper@pitt.edu
item_issues_count: 0
eprint_status: archive
creators_name: Napper, Andrew Michael
creators_email: napper@pitt.edu
creators_id: NAPPER
title: Electron Transfer through Thin Organic Films and Highly Curved Donor-Bridge-Acceptor Molecules.
ispublished: unpub
divisions: sch_as_chemistry
full_text_status: public
keywords: C-Clamp; DBA; electrochemistry; electron transfer; photoinduced
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.
date: 2003-03-10
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: Walker, Gilbert C
etdcommittee_name: Jordan, Kenneth D
etdcommittee_name: Zimmt, Matthew B
etdcommittee_email: dave@pitt.edu
etdcommittee_email: gilbertw@pitt.edu
etdcommittee_email: jordan@pitt.edu
etdcommittee_email: Matthew_Zimmt@brown.edu
etdcommittee_id: DAVE
etdcommittee_id: GILBERTW
etdcommittee_id: JORDAN
etdcommittee_id: 
etd_defense_date: 2002-08-30
etd_approval_date: 2003-03-10
etd_submission_date: 2002-09-05
etd_access_restriction: immediate
etd_patent_pending: FALSE
assigned_doi: doi:10.5195/pitt.etd.2011.9329
thesis_type: dissertation
degree: PhD
committee: Prof. David H. Waldeck (dave@pitt.edu) - Committee Chair
committee: Prof. Gilbert C. Walker (gilbertw@pitt.edu) - Committee Member
committee: Prof. Kenneth D. Jordan (jordan@pitt.edu) - Committee Member
committee: Prof. Matthew B. Zimmt (Matthew_Zimmt@brown.edu) - Committee Member
etdurn: etd-09052002-115124
other_id: http://etd.library.pitt.edu:80/ETD/available/etd-09052002-115124/
other_id: etd-09052002-115124
citation:   Napper, Andrew Michael  (2003) Electron Transfer through Thin Organic Films and Highly Curved Donor-Bridge-Acceptor Molecules.  Doctoral Dissertation, University of Pittsburgh.    (Unpublished)  
document_url: http://d-scholarship-dev.library.pitt.edu/9329/1/thesis2.pdf