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Jahn–Teller Effect in Molecular Magnetism: An Overview

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The Jahn-Teller Effect

Part of the book series: Springer Series in Chemical Physics ((CHEMICAL,volume 97))

Abstract

In this article we review applications of the concepts of the Jahn–Teller effect in molecular magnetism. The scope of the contemporary field of molecular magnetism and its fascinating applications are shortly described. The theoretical background of molecular magnetism as well as the applications of molecular magnets are closely related to the basic concepts of the Jahn–Teller effect through their structural properties affecting magnetic anisotropy, interaction with light, photo-induced magnetism, co-operative behavior of molecule-based magnetic systems, and dynamical properties affected by relaxation processes and spin coherence times.

We show that a wide class of symmetric spin-frustrated systems are orbitally degenerate, and the Jahn–Teller effect plays an important role in the description of their properties. In high-nuclearity magnetic clusters (single molecule magnets) the Jahn–Teller coupling stabilizes a specific alignment of the local magnetic axes, giving rise to a global anisotropy and consequently to a spin reorientation barrier. The problem of the double exchange in mixed-valence systems is considered, with the emphasis on the underlying role of the pseudo Jahn–Teller coupling in localization/delocalization of the mobile electron. Under certain conditions the latter gives rise to a reduction of the double exchange and, in particular, reduces the magnetic anisotropy in the presence of orbital degeneracy. The properties of mixed-valence systems are closely related to a complicated interplay between the pseudo Jahn–Teller interaction, isotropic exchange and double exchange. Manifestations of the Jahn–Teller effect are discussed for a wide class of photoactive (photoswitchable) systems. Pseudo Jahn–Teller models are employed for the description of the tautomeric transformations and extremely long living metastable states in photochromic compounds. Finally, we review the problem of co-operative phenomena in molecule-based extended mixed-valence systems, for which the Jahn–Teller mechanism is shown to result in the charge and structural ordering. The concept of the Jahn–Teller effect combined with the so-called quasidynamical approach allows to describe the intervalence optical bands and to reveal the underlying physical mechanism (quantum resonances of the vibronic levels) of the intricate quantum phenomena of the coexistence of localized and delocalized states in crystals based on interacting mixed-valence units.

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Abbreviations

JTE:

Jahn–Teller effect

JT coupling:

Jahn–Teller coupling

SMM:

Single molecule magnets

MV:

Mixed-valency

AS exchange:

Antisymmetric exchange

HDVV model:

Heisenberg-Dirac-Van Vleck model

ITO:

Irreducible tensor operator

PKS model:

Piepho-Krausz-Schatz model

P-model:

Piepho model

SNP:

Sodium nitroprusside

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Acknowledgements

This review article is partially based on the results published in co-authorship with M. Belinsky, J.J. Borrás-Almenar, J.M. Clemente-Juan, E. Coronado, A. Müller, S. Ostrovsky, O. Reu, A. Tarantul. We thank our colleagues for the long-term collaboration and many fruitful discussions. Financial support from the German-Israeli Foundation for Scientific Research and Development (grant G-775–19.10/2003) and USA-Israel Binational Science Foundation (Grant No. 2006498) is gratefully acknowledged. Financial support from the Supreme Council for Science and Technological Development of Moldova is also appreciated.

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Authors and Affiliations

  1. Department of Chemistry, Ben-Gurion University of the Negev, 653, 84105, Beer-Sheva, Israel

    Boris Tsukerblat

  2. Institute of Applied Physics of the Academy of Sciences of Moldova, Academy str.5, Kishinev, 2028, Moldova

    Sophia Klokishner & Andrew Palii

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Correspondence to Boris Tsukerblat .

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  1. LS für Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, Heidelberg, 69120, Germany

    Horst Köppel

  2. Dept. Chemistry, Johns Hopkins University, Baltimore, 21218, U.S.A.

    David R. Yarkony

  3. MPI für Festkörperforschung, Heisenbergstr. 1, Stuttgart, 70569, Germany

    Heinz Barentzen

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Tsukerblat, B., Klokishner, S., Palii, A. (2009). Jahn–Teller Effect in Molecular Magnetism: An Overview. In: Köppel, H., Yarkony, D., Barentzen, H. (eds) The Jahn-Teller Effect. Springer Series in Chemical Physics, vol 97. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-03432-9_18

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