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Molecules 2013, 18(6), 6679-6722; doi:10.3390/molecules18066679

Isotope Effects in ESR Spectroscopy

1 Institute of Chemistry, Humboldt University of Berlin, Brook-Taylor-Str. 2, Berlin 12489, Germany 2 Institute of Pharmacy, Free University Berlin, Kelchstr. 31, Berlin 12169, Germany
* Author to whom correspondence should be addressed.
Received: 26 March 2013 / Revised: 14 May 2013 / Accepted: 29 May 2013 / Published: 7 June 2013
(This article belongs to the Special Issue Isotope Effects)
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In order to present the relationship between ESR spectroscopy and isotope effects three levels are considered: (i) ESR spectroscopy is described on a general level up to the models for interpretation of the experimental spectra, which go beyond the usually used time and mass independent spin-Hamilton operator, (ii) the main characteristics of the generalized isotope effects are worked out, and finally (iii) the basic, mainly quantum mechanical effects are used to describe the coupling of electron spins with the degrees of freedom, which are accessible under the selected conditions, of the respective paramagnetic object under investigation. The ESR parameters and the respective models are formalized so far, that they include the time and mass depending influences and reflect the specific isotope effects. Relations will be established between the effects in ESR spectra to spin relaxation, to spin exchange, to the magnetic isotope effect, to the Jahn-Teller effects, as well as to the influence of zero-point vibrations. Examples will be presented which demonstrate the influence of isotopes as well as the kind of accessible information. It will be differentiated with respect to isotope effects in paramagnetic centres itself and in the respective matrices up to the technique of ESR imaging. It is shown that the use of isotope effects is indispensable in ESR spectroscopy.
Keywords: effects of nuclear spin; mass dependency; magnetic moment; local symmetry; time dependency; vibronics and tunnelling in ESR effects of nuclear spin; mass dependency; magnetic moment; local symmetry; time dependency; vibronics and tunnelling in ESR
This is an open access article distributed under the Creative Commons Attribution License (CC BY) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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Stößer, R.; Herrmann, W. Isotope Effects in ESR Spectroscopy. Molecules 2013, 18, 6679-6722.

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