title: Predicting accurate electronic excitation transfer rates via marcus theory with Boys or Edmiston-Ruedenberg localized diabatization.
abstract: We model the triplet-triplet energy-transfer experiments from the Closs group [ Closs , G. L. ; et al. J. Am. Chem. Soc. 1988 , 110 , 2652. ] using a combination of Marcus theory and either Boys or Edmiston-Ruedenberg localized diabatization, and we show that relative and absolute rates of electronic excitation transfer may be computed successfully. For the case where both the donor and acceptor occupy equatorial positions on a rigid cyclohexane bridge, we find beta(calc) = 2.8 per C-C bond, compared with the experimental value beta(exp) = 2.6. This work highlights the power of using localized diabatization methods as a tool for modeling nonequilibrium processes.
authors.affiliation: Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA. subotnik@sas.upenn.edu
authors.forename: Joseph E
authors.initials: JE
authors.lastname: Subotnik
authors.forename: Josh
authors.initials: J
authors.lastname: Vura-Weis
authors.forename: Alex J
authors.initials: AJ
authors.lastname: Sodt
authors.forename: Mark A
authors.initials: MA
authors.lastname: Ratner
mesh_terms: D001547:Benzaldehydes / Q000737:chemistry*; D003198:Computer Simulation; D004583:Electrons; D015394:Molecular Structure; D009281:Naphthalenes / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D001547:Benzaldehydes; D009281:Naphthalenes; C032175:benzaldehyde
references.citation: Proc Natl Acad Sci U S A. 1974 Jun;71(6):2265-7
references.pmid: 16592157
references.citation: J Phys Chem B. 2009 May 14;113(19):6583-99
references.pmid: 19331333
references.citation: Acc Chem Res. 2009 Apr 21;42(4):509-18
references.pmid: 19215069
references.citation: J Chem Phys. 2008 Aug 28;129(8):084708
references.pmid: 19044842
references.citation: J Chem Phys. 2009 Jun 21;130(23):234102
references.pmid: 19548706
references.citation: Phys Chem Chem Phys. 2006 Jul 21;8(27):3172-91
references.pmid: 16902710
references.citation: J Chem Phys. 2004 Nov 15;121(19):9220-9
references.pmid: 15538842
references.citation: J Chem Phys. 2008 Dec 28;129(24):244101
references.pmid: 19123489