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Theoretical Treatment of Degenerate Electron Exchange and Dimerization in Spin Dynamics of Radical Ion Pairs as Observed by Magnetic Field Effects

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Abstract

In this work we have compared manifestations of degenerate electron exchange (DEE) and dimerization reactions in MARY (magnetically affected reaction yield) spectroscopy and time-resolved magnetic field effects (TR-MFE) of radical ion pairs (RIPs). It is shown that dimerization results in phase and frequency changes of the quantum beats in TR-MFE traces, whereas DEE leads to relaxation-type changes in the spin dynamics of RIPs. Dimerization does not change the width of MARY lines considerably, but leads to new lines corresponding to dimer radical ions. In contrast, DEE substantially changes the MARY line widths. Our treatment provides ways to discriminate between both processes from experimental MARY spectra and TR-MFE kinetics. An experimental example dealing with concentration-dependent broadening of the MARY lines is also discussed.

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Acknowledgments

Financial support by the Russian Foundation for Basic Research (project nos.11-03-00356, 11-03-00296, 12-03-00238, and 12-03-33082), the Program of the President of the Russian Federation for the support of leading scientific schools (project nos. NSch-7643.2010.3, and NSch-2272.2012.3), the Interdisciplinary project no. 71 of the Siberian Branch of the Russian Academy of Sciences, and the Program P-220 of the Russian Government (grant no. 11.G34.31.0045) is gratefully acknowledged.

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Authors and Affiliations

  1. International Tomography Center, Siberian Branch, Russian Academy of Sciences, Institutskaya ul. 3a, Novosibirsk, 630090, Russia

    Konstantin L. Ivanov & Nikita N. Lukzen

  2. Novosibirsk State University, Novosibirsk, 630090, Russia

    Konstantin L. Ivanov, Dmitri V. Stass, Evgeny V. Kalneus, Robert Kaptein & Nikita N. Lukzen

  3. Institute of Chemical Kinetics and Combustion, Siberian Branch, Russian Academy of Sciences, Institutskaya ul. 3, Novosibirsk, 630090, Russia

    Dmitri V. Stass & Evgeny V. Kalneus

  4. Bijvoet Center, Utrecht University, Padualaan 8, 3584 CH, Utrecht, The Netherlands

    Robert Kaptein

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  1. Konstantin L. Ivanov
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Correspondence to Konstantin L. Ivanov.

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Ivanov, K.L., Stass, D.V., Kalneus, E.V. et al. Theoretical Treatment of Degenerate Electron Exchange and Dimerization in Spin Dynamics of Radical Ion Pairs as Observed by Magnetic Field Effects. Appl Magn Reson 44, 217–232 (2013). https://doi.org/10.1007/s00723-012-0413-y

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  • DOI: https://doi.org/10.1007/s00723-012-0413-y

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