?url_ver=Z39.88-2004&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Adc&rft.relation=http%3A%2F%2Fd-scholarship-dev.library.pitt.edu%2F6684%2F&rft.title=SOLVENT+MEDIATED+ELECTRON+TRANSFER+IN+C-CLAMP+SHAPED+MOLECULES&rft.creator=Read%2C+Ian+Anthony&rft.description=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%2C+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%2C+the+dependence+of+the+electron+transfer+rate+on+solvent+position+is+evaluated.+These+results+are+consistent+with+a+temperature+dependent+electronic+coupling+mechanism.&rft.date=2009-06-22&rft.type=University+of+Pittsburgh+ETD&rft.type=PeerReviewed&rft.format=application%2Fpdf&rft.language=en&rft.identifier=http%3A%2F%2Fd-scholarship-dev.library.pitt.edu%2F6684%2F1%2FReadPhD021720092.pdf&rft.identifier=++Read%2C+Ian+Anthony++(2009)+SOLVENT+MEDIATED+ELECTRON+TRANSFER+IN+C-CLAMP+SHAPED+MOLECULES.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++