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Solvent dynamical effects on electron transfer in U-shaped donor-bridge-acceptor molecules.
MedLine Citation:
PMID:  19146395     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
This study explores how the electron transfer in a class of donor-bridge-acceptor (DBA) supermolecules is affected by the dynamical response of the solvent. These DBA molecules have a pendant group juxtaposed between the donor and acceptor groups (Figure 1). The pendant provides intermediate electronic coupling strengths of a few hundred wavenumbers by way of its nonbonded contacts with the donor and acceptor and it can be tuned by substituents added to the pendant. This design allows the measurement of electron transfer rates from a regime in which the mechanism is nonadiabatic to a regime in which the solvent friction modifies the rate substantially. The rate constants and mechanistic parameters are compared with the expectations of models for solvent dynamical effects on the reaction rate.
Authors:
Subhasis Chakrabarti; Min Liu; David H Waldeck; Anna M Oliver; Michael N Paddon-Row
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  113     ISSN:  1520-5215     ISO Abbreviation:  J Phys Chem A     Publication Date:  2009 Feb 
Date Detail:
Created Date:  2009-02-05     Completed Date:  2009-04-08     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  United States    
Other Details:
Languages:  eng     Pagination:  1040-8     Citation Subset:  -    
Affiliation:
Chemistry Department, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
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