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Vujosevi Cacute D, Dilger H, McKenzie I, et al. Local ordering in liquids: solvent effects on the hyperfine couplings of the cyclohexadienyl radical. J Phys Chem B. 2007;111(1):199-208doi: 10.1021/jp065488q.
Vujosevi Cacute, D., Dilger, H., McKenzie, I., Martyniak, A., Scheuermann, R., & Roduner, E. (2007). Local ordering in liquids: solvent effects on the hyperfine couplings of the cyclohexadienyl radical. The journal of physical chemistry. B, 111(1), 199-208. https://doi.org/10.1021/jp065488q
Vujosevi Cacute, Danilo, et al. "Local ordering in liquids: solvent effects on the hyperfine couplings of the cyclohexadienyl radical." The journal of physical chemistry. B vol. 111,1 (2007): 199-208. doi: https://doi.org/10.1021/jp065488q
Vujosevi Cacute D, Dilger H, McKenzie I, Martyniak A, Scheuermann R, Roduner E. Local ordering in liquids: solvent effects on the hyperfine couplings of the cyclohexadienyl radical. J Phys Chem B. 2007 Jan 11;111(1):199-208. doi: 10.1021/jp065488q. PMID: 17201444.
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J Phys Chem B. 2007 Jan 11;111(1):199-208. doi: 10.1021/jp065488q.

Local ordering in liquids: solvent effects on the hyperfine couplings of the cyclohexadienyl radical.

The journal of physical chemistry. B

Danilo Vujosevi Cacute, Herbert Dilger, Iain McKenzie, Aleksandra Martyniak, Robert Scheuermann, Emil Roduner

Affiliations

  1. Institut für Physikalische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany.

PMID: 17201444 DOI: 10.1021/jp065488q

Abstract

Ordering of solvent molecules in the vicinity of a dipolar free radical affects its hyperfine coupling constants (hfcs). Specifically, it is demonstrated how the variation of the experimental methylene proton and muon hfcs of the muoniated cyclohexadienyl radical in several solvents and solvent mixtures of varying polarity can be accounted for by a dipole-dipole reaction field model that is based on the model of Reddoch and Konishi (J. Chem. Phys. 1979, 70, 2121) which was developed to explain the solvent dependence of the 14N hfc in the di-tert-butyl-nitroxide radical. Ab initio calculations were carried out with the cyclohexadienyl radical in an electric field to model the electric field arising from the electric dipole moments of the surrounding solvent molecules. An extension of the model that includes the dipole-quadrupole interaction can account for the larger hfc in benzene compared with that in octadecane, and it is predicted that the hfc will be proportional to the concentration of quadrupole moments to the 4/3 power. The influence of hydrogen bonding between the radicals' pi electrons and the OH groups of the solvent on the hfcs is also discussed. Comparison with gas-phase data permits a separation of vibrational effects and reveals that approximately 28% of the temperature dependence in water is due to increasing solvent disorder.

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