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Zeitschrift für Physikalische Chemie

International journal of research in physical chemistry and chemical physics

Editor-in-Chief: Rademann, Klaus

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Volume 231, Issue 2


The Quantum Dynamical Basis of a Classical Kinetic Scheme Describing Coherent and Incoherent Regimes of Radical Pair Recombination

Nikita N. Lukzen
  • Novosibirsk State University, Pirogova Str. 2, and International Tomography Center, Siberian Branch Russian Academy of Science, Institutskaya 3a, Novosibirsk 630090, Russian Federation
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Johannes H. Klein
  • Institut für Organische Chemie, Wilhelm Conrad Röntgen Research Center for Complex Material Systems, Center for Nanosystems Chemistry, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Christoph Lambert
  • Institut für Organische Chemie, Wilhelm Conrad Röntgen Research Center for Complex Material Systems, Center for Nanosystems Chemistry, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Ulrich E. Steiner
Published Online: 2016-09-24 | DOI: https://doi.org/10.1515/zpch-2016-0833


In recent work from this group (J. H. Klein et al. J. Am. Chem. Soc. 2015, 137, 11011), the magnetic field dependent charge recombination kinetics in donor/Ir-complex/acceptor triads has been determined with outstanding accuracy and reproducibility. The field-dependent kinetics has been analyzed in terms of a classical reaction scheme including the field-independent rate parameters of singlet recombination (rate constant kS) and S/T0 mixing (rate constant kST0) and the field-dependent rate constant k±(B) connecting central and outer Zeeman levels. In the present work, the extraction of k± from the experimental data is more precisely defined and the appearance of a “coherent” and “incoherent” regime of spin motion in a double log plot of k± vs. B is confirmed. The experimental decay curves have been reproduced by a full quantum dynamical model based on the stochastic Liouville equation, which was solved numerically, taking into account isotropic hyperfine coupling with five nuclear spins (1 N on donor radical, 4 H on acceptor radical) and anisotropic hyperfine coupling with the nitrogen nucleus at the donor radical. The results of the quantum calculations serve as a rigorous basis of interpreting the classical parameter k±. Furthermore, it is demonstrated that the incoherent part of spin motion is essential for a full understanding of the charge recombination kinetics even in the “coherent” regime.

Keywords: charge recombination; linked radical pairs; spin chemistry; spin relaxation

Dedicated to: Professor Kev Salikhov on the occasion of his 80th birthday.


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About the article

aPresent address: UMR 5249 (Unité Mixte de Recherche) – LCBM – BIG – CEA, 17 Rue des Martyrs, 38054 Grenoble, France

Received: 2016-06-18

Accepted: 2016-08-17

Published Online: 2016-09-24

Published in Print: 2017-02-01

Citation Information: Zeitschrift für Physikalische Chemie, Volume 231, Issue 2, Pages 197–223, ISSN (Online) 2196-7156, ISSN (Print) 0942-9352, DOI: https://doi.org/10.1515/zpch-2016-0833.

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