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Weak exchange interactions in biradicals: A pseudopotential for unpaired electrons and an asymptotic methods for calculating the exchange integral

  • Elementary Physicochemical Processes
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Abstract

A theory of weak exchange interactions in biradicals is developed. The basic idea is to describe the motion of two weakly bound electrons on paramagnetic centers by a two-particle Schröbinger equation that takes into account the interaction of these electrons with the closed electron shells of the biradical, described by a model local potential, and their mutual Coulomb repulsion. The model potential can be constructed using the pseudopotential method, based on results of ab initio quantum chemical calculations. The exchange interaction between the unpaired electrons on the paramagnetic centers is calculated by a generalized asymptotic method that takes into account the quasi-classical nature of the subbarrier motion of the electrons in the region between the paramagnetic centers. The developed theory makes it possible to estimate the magnitude of the exchange interaction and to determine how this interaction depends on the distance between the paramagnetic centers and their relative orientation.

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References

  1. V. N. Parmon, A. I. Kokorin, and G. M. Zhidomirov, Stable Biradicals (Nauka, Moscow, 1980) [in Russian].

    Google Scholar 

  2. V. A. Tran, K. Rasmussen, G. Grampp, and A. I. Kokorin, Appl. Magn. Reson. 32, 395 (2007).

    Article  CAS  Google Scholar 

  3. Distance Measurements in Biological Systems by EPR, Ed. by L. J. Berliner, G. R. Eaton, and S. S. N. Y. Eaton (Kluwer Academic, Plenum, New York, 2000).

    Google Scholar 

  4. A. I. Kokorin, Appl. Magn. Reson. 26, 253 (2004).

    Article  CAS  Google Scholar 

  5. K. Higashiguchi, K. Yumoto, and K. Matsuda, Org. Lett. 12, 5284 (2010).

    Article  CAS  Google Scholar 

  6. E. A. Weiss, M. J. Ahrens, L. E. Sinks, et al., J. Am. Chem. Soc. 126, 5577 (2004).

    Article  CAS  Google Scholar 

  7. W. Wang, S. Wang, X. Li, et al., J. Am. Chem. Soc. 132, 8774 (2010).

    Article  CAS  Google Scholar 

  8. E. Pardo, J. Faus, M. Julve, et al., J. Am. Chem. Soc. 125, 10770 (2003).

    Article  CAS  Google Scholar 

  9. S. A. Wolf, D. D. Awschalom, R. A. Buhrman, et al., Science 294, 1488 (2001).

    Article  CAS  Google Scholar 

  10. E. Coronado, F. Palacios, and J. Veciana, Ang. Chem. Int. Ed. 42, 2570 (2003).

    Article  CAS  Google Scholar 

  11. V. Mereacre, M. Nakano, J. Gómez, et al., Chem. Eur. J. 12, 9238 (2006).

    Article  Google Scholar 

  12. S. Sanvito and A. R. Rocha, J. Comput. Theor. Nanosci. 3, 624 (2006).

    CAS  Google Scholar 

  13. EPR of Free Radicals in Solids II: Trends in Methods and Applications, Ed. by A. Lund and M. Shiotani (Springer, Dordrecht, Heidelberg, New York, London, 2013).

    Google Scholar 

  14. P. A. M. Dirac, The Principles of Quantum Mechanics (Clarendon, Oxford, 1958; Nauka, Moscow, 1979).

    Google Scholar 

  15. M. Diatkina and J. Syrkin, Acta Physicochim. U.R.S.S. 25, 23 (1946).

    Google Scholar 

  16. H. S. Jarrett, G. J. Sloan, and W. R. Vaughan, J. Chem. Phys. 25, 697 (1956).

    Article  CAS  Google Scholar 

  17. J. Grafenstein, E. Kraka, M. Filatov, and D. Cremer, Int. J. Mol. Sci. 3, 360 (2002).

    Article  Google Scholar 

  18. I. P. R. Moreira and F. Illas, Phys. Chem. Chem. Phys. 8, 1645 (2006).

    Article  CAS  Google Scholar 

  19. O. Kwon and G.-S. Chung, Bull. Korean Chem. Soc. 29, 2140 (2008).

    Article  CAS  Google Scholar 

  20. S. Nishizawa, J. Hasegawa, and K. Matsuda, Chem. Phys. Lett. 555, 187 (2013).

    Article  CAS  Google Scholar 

  21. H. M. McConnel, J. Chem. Phys. 33, 115 (1960).

    Article  Google Scholar 

  22. S. Ya. Umanskiy, E. N. Golubeva, and B. N. Plakhutin, Russ. Chem. Bull. 62, 1511 (2013).

    Article  CAS  Google Scholar 

  23. E. E. Nikitin and S. Ya. Umanskiy, Theory of Slow Atomic Collisions (Springer, Berlin, Heidelberg, 1984).

    Book  Google Scholar 

  24. J. D. Weeks, A. Hazi, and S. A. Rice, Adv. Chem. Phys. 16, 283 (1969).

    CAS  Google Scholar 

  25. P. Giannozzi, http://www.fisica.uniud.it/~giannozz

  26. D. H. Pereira, A. F. Ramos, N. H. Morgon, and R. Custodio, J. Chem. Phys. 135, 034106 (2011).

    Article  Google Scholar 

  27. A Primer in Density-Functional Theory, Ed. by C. Fiolhais, F. Nogueira, and M. A. L. Marques, Lecture Notes in Physics, Vol. 620 (Springer, Berlin, 2003).

    Google Scholar 

  28. M. A. Kozhushner and G. K. Ivanov, Chem. Phys. 170, 303 (1993).

    Article  Google Scholar 

  29. M. A. Kozhushner, K. Ya. Burshtein, G. K. Ivanov, and V. S. Posvyanskii, J. Exp. Theor. Phys. 82, 32 (1996).

    Google Scholar 

  30. L. P. Gor’kov and L. P. Pitaevskii, Sov. Phys. Dokl. 8, 788 (1963).

    Google Scholar 

  31. C. Herring and M. Flicker, Phys. Rev. A 134, 362 (1964).

    Article  CAS  Google Scholar 

  32. B. M. Smirnov and M. I. Chibisov, Sov. Phys. JETP 21, 624 (1965).

    Google Scholar 

  33. S. Ya. Umanskii and A. I. Voronin, Theor. Chim. Acta 12, 166 (1968).

    Article  CAS  Google Scholar 

  34. O. Bouty, G. Hadinger, and M. Aubert-Frecon, J. Mol. Struct. 330, 97 (1995).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia

    S. Ya. Umanskii

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Correspondence to S. Ya. Umanskii.

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Original Russian Text © S.Ya. Umanskii, 2015, published in Khimicheskaya Fizika, 2015, Vol. 34, No. 1, pp. 3–10.

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Umanskii, S.Y. Weak exchange interactions in biradicals: A pseudopotential for unpaired electrons and an asymptotic methods for calculating the exchange integral. Russ. J. Phys. Chem. B 9, 1–8 (2015). https://doi.org/10.1134/S1990793115010121

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  • DOI: https://doi.org/10.1134/S1990793115010121

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