title: Further evidence of an inverted region in proton transfer within the benzophenone/substituted aniline contact radical ion pairs; importance of vibrational reorganization energy.
abstract: The dynamics of proton transfer within the triplet contact radical ion pair of a variety of substituted benzophenones with N,N-diethylaniline, N,N-dimethyl-p-toluinide, and N,N-diallylaniline are examined in solvents of varying polarity. The correlation of the rate constants with driving force reveal both a normal region and an inverted region providing support for the nonadiabatic nature of proton transfer within these systems. The reorganization of both the solvent and the molecular framework are central in governing the overall reaction dynamics.
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA.
authors.forename: Libby R
authors.initials: LR
authors.lastname: Heeb
authors.forename: Kevin S
authors.initials: KS
authors.lastname: Peters
mesh_terms: D000498:Allyl Compounds / Q000737:chemistry; D000814:Aniline Compounds / Q000737:chemistry*; D001577:Benzophenones / Q000737:chemistry*; D004735:Energy Transfer; D005609:Free Radicals / Q000737:chemistry*; D008958:Models, Molecular; D011522:Protons; D012997:Solvents / Q000737:chemistry*; D013816:Thermodynamics; D014052:Toluidines / Q000737:chemistry; D014732:Vibration
chemical_list: D000498:Allyl Compounds; D000814:Aniline Compounds; D001577:Benzophenones; D005609:Free Radicals; D011522:Protons; D012997:Solvents; D014052:Toluidines; C047723:benzophenone; C015835:dimethyl-4-toluidine; C085691:2,6-diethylaniline