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Quantum Chemical Calculations of the Zero-Field Splitting Tensors for Organic Spin Multiplets

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EPR of Free Radicals in Solids I

Part of the book series: Progress in Theoretical Chemistry and Physics ((PTCP,volume 24))

Abstract

In this chapter the state-of-the-art quantum chemical methods for zero-field splitting (ZFS) tensors (D tensors) of organic high spin multiplets are reviewed. Both spin–spin dipolar (D SS) and spin–orbit (D SO) coupling terms appearing in the first and second order, respectively, in the perturbation theory starting from the non-relativistic Schrödinger equation are focused on. Theoretical frameworks for the D SS and D SO tensors in terms of ab initio molecular orbital theory and density functional theory (DFT) are outlined, and several examples of the D SS and D SO tensor calculations including spin–orbit coupling dominant systems (D SO≫D SS), electronic ground states of organic high-spin systems (spin-quintet and septet species), excited triplet states of closed-shell molecules, and a thermally accessible excited triplet state of quinonoidal dinitrene are given, emphasizing that they all have given testing grounds for the theoretical treatment of D tensors.

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Acknowledgments

This work has been supported by Grants-in-Aid for Scientific Research (B) and Scientific Research on Innovative Areas, “Quantum Cybernetics” from MEXT, Japan. The support by JST through Core Research for Evolutional Science and Technology (CREST) project, “Implementation of Molecular Spin Quantum Computers” and the support by the Funding Program for World-Leading Innovative R&D on Science and Technology (FIRST) project on “Quantum Information Processing”, JSPS, Japan are also acknowledged.

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Authors and Affiliations

  1. Department of Chemistry and Molecular Materials Science, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Osaka, 558-8585, Japan

    Kenji Sugisaki, Kazuo Toyota, Kazunobu Sato, Daisuke Shiomi & Takeji Takui

  2. Department of System Innovation, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka, 560-8531, Japan

    Masahiro Kitagawa

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  1. Kenji Sugisaki
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  2. Kazuo Toyota
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Correspondence to Takeji Takui .

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  1. The Emeritus Academy, Department of Physics, Chemistry and Bio, Linkoping University, Linkoping, SE-581 83, Sweden

    Anders Lund

  2. Graduate School of Engineering, Hiroshima University, 4-26-8 Takamigaoka, Takaya, Higashi-Hiroshima, 739-2115, Japan

    Masaru Shiotani

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Sugisaki, K., Toyota, K., Sato, K., Shiomi, D., Kitagawa, M., Takui, T. (2013). Quantum Chemical Calculations of the Zero-Field Splitting Tensors for Organic Spin Multiplets. In: Lund, A., Shiotani, M. (eds) EPR of Free Radicals in Solids I. Progress in Theoretical Chemistry and Physics, vol 24. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-4893-4_8

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