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Journal

2015 | 60 | 3 | 377-383

Article title

EMR-related problems at the interface between the crystal field Hamiltonians and the zero-field splitting Hamiltonians

Content

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Languages of publication

EN

Abstracts

EN
The interface between optical spectroscopy, electron magnetic resonance (EMR), and magnetism of transition ions forms the intricate web of interrelated notions. Major notions are the physical Hamiltonians, which include the crystal field (CF) (or equivalently ligand field (LF)) Hamiltonians, and the effective spin Hamiltonians (SH), which include the zero-field splitting (ZFS) Hamiltonians as well as to a certain extent also the notion of magnetic anisotropy (MA). Survey of recent literature has revealed that this interface, denoted CF (LF) ↔ SH (ZFS), has become dangerously entangled over the years. The same notion is referred to by three names that are not synonymous: CF (LF), SH (ZFS), and MA. In view of the strong need for systematization of nomenclature aimed at bringing order to the multitude of different Hamiltonians and the associated quantities, we have embarked on this systematization. In this article, we do an overview of our efforts aimed at providing a deeper understanding of the major intricacies occurring at the CF (LF) ↔ SH (ZFS) interface with the focus on the EMR-related problems for transition ions.

Publisher

Journal

Year

Volume

60

Issue

3

Pages

377-383

Physical description

Dates

published
1 - 7 - 2015
received
29 - 4 - 2014
accepted
30 - 1 - 2015
online
6 - 8 - 2015

Contributors

  • Institute of Physics, West Pomeranian University of Technology, 17 Piastów Ave., 70-310 Szczecin, Poland; Since 1 March 2015 Visiting Professor, Faculty of Chemistry, Adam Mickiewicz University, 89B Umultowska Str., 61-614 Poznań, Poland
  • Faculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie Str., 50-383 Wrocław, Poland

References

  • 1. Figgis, B. N., & Hitchman, M. A. (2000). Ligand field theory and its applications. New York: Wiley-VCH.
  • 2. Mulak, J., & Gajek, Z. (2000). The effective crystal field potential. Amsterdam: Elsevier.
  • 3. Newman, D. J., & Ng, B. (Eds.) (2000). Crystal field handbook. Cambridge: Cambridge University Press.
  • 4. Wildner, M., Andrut, M., & Rudowicz, C. (2004). Optical absorption spectroscopy in geosciences. Part I: Basic concepts of crystal field theory. In A. Beran & E. Libowitzky (Eds.), Spectroscopic methods in mineralogy – European Mineralogical Union Notes in Mineralogy. (Vol. 6, Chapter 3, pp. 93–143). Budapest: Eötvös University Press.
  • 5. Liu, G., & Jacquier, B. (Eds.). (2005). Spectroscopic properties of rare earths in optical materials. Berlin: Tsinghua University Press and Springer.
  • 6. Weil, J. A., Bolton, J. R., & Wertz, J. E. (1994). Electron paramagnetic resonance, elemental theory and practical applications. New York: Wiley.
  • 7. Bencini, A., & Gatteschi, D. (1990). EPR of exchange coupled systems. Berlin: Springer.
  • 8. Mabbs, F. E., & Collison, D. (1992). Electron paramagnetic resonance of d transition-metal compounds. Amsterdam: Elsevier.
  • 9. Misra, S. K. (Ed.) (2011). Multifrequency electron paramagnetic resonance. Weinheim: Wiley-VCH.
  • 10. Boča, R. (1999). Theoretical foundations of molecular magnetism. Amsterdam: Elsevier.
  • 11. Buschow, K. H. J., & de Boer, F. R. (2003). Physics of magnetism and magnetic materials. New York: Kluwer Academic.
  • 12. Boča, R. (2006). Magnetic parameters and magnetic functions in mononuclear complexes beyond the spin-Hamiltonian formalism. Struct. Bond., 117, 1–264.
  • 13. Gatteschi, D., Sessoli, R., & Villain, J. (2006). Molecular nanomagnets. Oxford: Oxford University Press.
  • 14. Rudowicz, C., & Karbowiak, M. (2014). Terminological confusions and problems at the interface between the crystal field Hamiltonians and the zero-field splitting Hamiltonians – survey of the CF=ZFS confusion in recent literature. Physica B, 451, 134–150.
  • 15. Rudowicz, C., & Karbowiak, M. (2015). Revealing the consequences and errors of substance arising from the inverse confusion between the crystal (ligand) field quantities and the zero-field splitting ones. Physica B, 456, 330–338.
  • 16. Sorace, L., Benelli, C., & Gatteschi, D. (2011). Lanthanides in molecular magnetism: old tools in a new field. Chem. Soc. Rev., 40, 3092–3104.[Crossref]
  • 17. Rudowicz, C., & Karbowiak, M. (2015). Disentangling intricate web of interrelated notions at the interface between the physical (crystal field) Hamiltonians and the effective (spin) Hamiltonians. Coord. Chem. Rev., 287, 28–63.
  • 18. Baldoví, J. J., Cardona-Serra, S., Clemente-Juan, J. M., Coronado, E., Gaita-Arino, A., & Palii, A. (2013). SIMPRE: A software package to calculate crystal field parameters, energy levels, and magnetic properties on mononuclear lanthanoid complexes based on charge distributions. J. Comput. Chem., 34, 1961–1967.[Crossref]
  • 19. Pandey, S., & Kripal, R. (2013). Zero-field splitting parameters of Cr3+ in lithium potassium sulphate at orthorhombic symmetry site. Acta Phys. Pol. A, 123, 101–105.
  • 20. Rudowicz, C., & Karbowiak, M. (2014). Implications of invalid conversions between crystal-field splitting ones used in superposition model. Acta Phys. Pol. A, 125, 1215–1219.
  • 21. Karbowiak, M., & Rudowicz, C. (2014). Software package SIMPRE – revisited. J. Comput. Chem., 35, 1935–1941.[Crossref]
  • 22. Solano-Peralta, A., Sosa-Torres, M. E., Flores-Alamo, M., El-Mkami, H., Smith, G. M., Toscano, R. A., & Nakamura, T. (2004). High-field EPR study and crystal and molecular structure of trans-RSSR-[CrCl2 (cyclam).] nX (X = ZnCl 42−, Cl− and Cl−·4H2O·0.5HCl). Dalton Trans., 2004, 2444–2449.
  • 23. Kowalczyk, R. M., Kemp, T. F., Walker, D., Pike, K. J., Thomas, P. A., Kreisel, J., Dupree, R., Newton, M. E., Hanna, J. V., & Smith, M. E. (2011). A variable temperature solid-state nuclear magnetic resonance, electron paramagnetic resonance and Raman scattering study of molecular dynamics in ferroelectric fluorides. J. Phys.-Condens. Matter, 23, 315402(16pp).[Crossref]
  • 24. Muralidhara, R. S., Kesavulu, C. R., Rao, J. L., Anavekar, R. V., & Chakradhar, R. P. S. (2010). EPR and optical absorption studies of Fe3+ ions in sodium borophosphate glasses. J. Phys. Chem. Solids, 71, 1651–1655.
  • 25. Padlyak, B. V., Wojtowicz, W., Adamiv, V. T., Burak, Y. V., & Teslyuk, I. M. (2010). EPR spectroscopy of the Mn2+ and Cu2+ centres in lithium and potassium-lithium tetraborate glasses. Acta Phys. Pol. A, 117, 122–125.
  • 26. Singh, R. K., & Srinivasan, A. (2010). EPR and magnetic susceptibility studies of iron ions in ZnOFe2 O3-SiO2-CaO-P2O5-Na2O glasses. J. Magn. Magn. Mater., 322, 2018–2022.
  • 27. Antal, A., Janossy, A., Forro, L., Vertelman, E. J. M., van Koningsbruggen, P. J., & van Loosdrecht, P. H. M. (2010). Origin of the ESR spectrum in the Prussian blue analog RbMn[Fe(CN)6]·H2O. Phys. Rev. B, 82, 14422(5pp).
  • 28. Nagy, K. L., Quintavalle, D., Feher, T., & Janossy, A. (2011). Multipurpose high-frequency ESR spectrometer for condensed matter research. Appl. Magn. Reson., 40, 47–63.[Crossref]
  • 29. Nagy, K. L., Náfrádi, B., Kushch, N. D., Yagubskii, E. B., Herdtweck, E., Fehér, T., Kiss, L. F., Forró, L., & Jánossy, A. (2009). Multifrequency ESR in ET2 MnCu[N(CN)2]4: A radical cation salt with quasi-two-dimensional magnetic layers in a three-dimensional polymeric structure. Phys. Rev. B, 80, 104407(8pp).
  • 30. Aleshkevych, P., Fink-Finowicki, J., Gutowski, M., & Szymczak, H. (2010). EPR of Mn2+ in the kagomé staircase compound Mg2.97Mn0.03V2O8. J. Magn. Reson., 205, 69–74.
  • 31. Garcia, F. A., Venegas, P. A., Pagliuso, P. G., Rettori, C., Fisk, Z., Schlottmann, P., & Oseroff, S. B. (2011). Thermally activated exchange narrowing of the Gd3+ ESR fine structure in a single crystal of Ce1-xGdxFe4P12 (x ≈ 0.001) skutterudite. Phys. Rev. B, 84, 125116(7pp).
  • 32. Güler, S., Rameev, B., Khaibullin, R. I., Lopatin, O. N., & Aktaş, B. (2010). EPR study of Mn-implanted single crystal plates of TiO2 rutile. J. Magn. Magn. Mater., 322, L13–L17.
  • 33. Schweiger, A., & Jeschke, G. (2001). Principles of pulse electron paramagnetic resonance. Oxford: Oxford University Press.
  • 34. Gerson, F., & Huber, W. (2003). Electron spin resonance spectroscopy of organic radicals. Weinheim: Wiley-VCH.
  • 35. Kaupp, M., Buhl, M., & Malkin, V. G. (2004). Calculation of NMR and EPR parameters. Weinheim: Wiley-VCH.
  • 36. Lushington, G. H. (2004). The effective spin Hamiltonian concept from a quantum chemical perspective. In M. Kaupp, M. Buhl & V. G. Malkin (Eds.), Calculation of NMR and EPR parameters (Chapter 4). Weinheim: Wiley-VCH.
  • 37. Neese, F. (2004). Zero-field splitting. In M. Kaupp, M. Buhl & V. G. Malkin (Eds.), Calculation of NMR and EPR parameters (Chapter 34). Weinheim: Wiley-VCH.
  • 38. Mobius, K., & Savitsky, A. (2009). High-field EPR spectroscopy on proteins and their model systems characterization of transient paramagnetic states. Cambridge: The Royal Society of Chemistry.
  • 39. Jeschke, G., & Schlick, S. (2006). Continuous-wave and pulsed ESR methods. In S. Schlick (Ed.), Advanced ESR methods in polymer research. New Jersey, USA: John Wiley & Sons.
  • 40. Rudowicz, C. (2008). Clarification of the confusion concerning the crystal-field quantities vs. the zero-field splitting quantities in magnetism studies: Part II – survey of literature dealing with model studies of spin systems. Physica B, 403, 2312–2330.
  • 41. Rudowicz, C., & Sung, H. W. F. (2001). Can the electron magnetic resonance (EMR) techniques measure the crystal (ligand) field parameters? Physica B, 300, 1–26.
  • 42. Rudowicz, C. (2009). Truncated forms of the second-rank orthorhombic Hamiltonians used in magnetism and electron magnetic resonance (EMR) studies are invalid – why it went unnoticed for so long? J. Magn. Magn. Mater., 321, 2946–2955.
  • 43. Rieger, P. H. (2007). Electron spin resonance analysis and interpretation. Cambridge: The Royal Society of Chemistry.
  • 44. Lund, A., Shiotani, M., & Shimada, S. (2011). Principles and applications of ESR spectroscopy. Dordrecht: Springer Science+Business Media B.V.
  • 45. Brustolon, M., & Giamello, E. (2009). Electron paramagnetic resonance: A practitioner’s toolkit. New Jersey, USA: John Wiley & Sons.
  • 46. Tang, J. K., Wang, Q. L., Si, S. F., Liao, D. Z., Jiang, Z. H., Yan, S. P., & Cheng, P. (2005). A novel tetranuclear lanthanide(III)-copper(II) complex of the macrocyclic oxamide [PrCu3](macrocyclic oxamide = 1,4,8,11-tetraazacyclotradecanne-2,3-dione): synthesis, structure and magnetism. Inorg. Chim. Acta, 358, 325–330.
  • 47. Li, B., Gu, W., Zhang, L. Z., Qu, J., Ma, Z. P., Liu, X., & Liao, D. Z. (2006). [Ln2(C2O4)2 (pyzc)2 (H2O)2]n[Ln = Pr (1), Er (2)]: Novel two-dimensional lanthanide coordination polymers with 2-pyrazinecarboxylate and oxalate. Inorg. Chem., 45, 10425–10427.[Crossref]
  • 48. Ouyang, Y., Zhang, W., Xu, N., Xu, G. F., Liao, D. Z., Yoshimura, K., Yan, S. P., & Cheng, P. (2007). Threedimensional 3d-4f polymers containing heterometallic rings: Syntheses, structures, and magnetic properties. Inorg. Chem., 46, 8454–8456.[Crossref]
  • 49. Xu, N., Shi, W., Liao, D. Z., Yan, S. P., & Cheng, P. (2008). Template synthesis of lanthanide (Pr, Nd, Gd) coordination polymers with 2-hydroxynicotinic acid exhibiting ferro-/antiferromagnetic interaction. Inorg. Chem., 47, 8748–8756.[Crossref]
  • 50. Hou, Y. L., Xiong, G., Shen, B., Zhao, B., Chen, Z., & Cui, J. Z. (2013). Structures, luminescent and magnetic properties of six lanthanide–organic frameworks: observation of slow magnetic relaxation behavior in the DyIII compound. Dalton Trans., 42, 3587–3596.
  • 51. AlDamen, M. A., Cardona-Serra, S., Clemente-Juan, J. M., Coronado, E., Martí-Gastaldo, C., Gaita-Arino, A., Luis, F., & Montero, O. (2009). Mononuclear lanthanide single molecule magnets based on the polyoxometalates [Ln(W5O18)2]9− and [Ln(β2-SiW11O39)2]13-(LnIII = Tb, Dy, Ho, Er, Tm, and Yb). Inorg. Chem., 48, 3467–3479.
  • 52. Luzon, J., Bernot, K., Hewitt, I. J., Anson, C. E., Powell, A. K., & Sessoli, R. (2008). Spin chirality in a molecular dysprosium: the archetype of the noncollinear ising model. Phys. Rev. Lett., 100, 247205(4pp).[Crossref]
  • 53. Bartolomé, J., Filoti, G., Kuncser, V., Schinteie, G., Mereacre, V., Anson, C. E., Powell, A. K., Prodius, D., & Turta, C. (2009). Magnetostructural correlations in the tetranuclear series of {Fe3LnO2} butterfly core clusters: magnetic and Mössbauer spectroscopic study. Phys. Rev. B, 80, 014430(16pp).
  • 54. Pointillart, F., Le Guennic, B., Golhen, S., Cador, O., Maury, O., & Ouahab, L. (2013). High nuclearity complexes of lanthanide involving tetrathiafulvalene ligands: structural, magnetic, and photophysical properties. Inorg. Chem., 52, 1610–1620.[Crossref]
  • 55. Bayrakçeken, F., Demir, O. J., & Karaaslan, İ. Ş. (2007). Theoretical investigations of the specific heat functions for the orthorhombic Nd+3 centers in some crystals. Spectrochim. Acta Part A, 66, 462–466.
  • 56. Bayrakçeken, F., Demir, O. J., & Karaaslan, İ. Ş. (2007). Specific heat functions for the orthorhombic Nd3+ in scheelite type of crystals. Spectrochim. Acta Part A, 66, 1291–1294.
  • 57. Kim, Y. H., Yeom, T. H., Eguchi, H., & Seidel, G. M. (2007). Magnetic properties of erbium in single crystal Bi2Te3. J. Magn. Magn. Mater., 310, 1703–1705.
  • 58. Pedersen, K. S., Ungur, L., Sigrist, M., Sundt, A., Schau-Magnussen, M., Vieru, V., Mutka, H., Rols, S., Weihe, H., Waldmann, O., Chibotaru, L. F., Bendix, J., & Dreiser, J. (2014). Modifying the properties of 4f single-ion magnets by peripheral ligand functionalisation. Chem. Sci., 5, 1650–1660.[Crossref]
  • 59. Rudowicz, C. (2008). Clarification of terminological confusion concerning the crystal field quantities vs the effective spin Hamiltonian and zero-field splitting quantities in the papers by Bayrakçeken et al. [Spectrochim. Acta Part A 66 (2007). 462 & 1291]. Spectrochim. Acta Part A, 71, 1623–1626.
  • 60. Baldoví, J. J., Cardona-Serra, S., Clemente-Juan, J. M., Coronado, A., Gaita-Ariñ o, A., & Palii, A. (2012). Rational design of single-ion magnets and spin qubits based on mononuclear lanthanoid complexes. Inorg. Chem., 51, 12565–12574.[Crossref]
  • 61. Baldoví, J. J., Borrás-Almenar, J. J., Clemente-Juan, J. M., Coronado, E., & Gaita-Ariño, A. (2012). Modeling the properties of lanthanoid single-ion magnets using an effective point-charge approach. Dalton Trans., 41, 13705–13710.
  • 62. Baldoví, J. J., Cardona-Serra, S., Clemente-Juan, J. M., Coronado, E., & Gaita-Ariño, A. (2013). Modeling the properties of uranium-based single ion magnets. Chem. Sci., 4, 938–946.[Crossref]
  • 63. Baldoví, J. J., Clemente-Juan, J. J., Coronado, E., & Gaita-Ariñ o, A. (2013). Two pyrazolylborate dysprosium(III) and neodymium(III), single ion magnets modeled by a radial effective charge approach. Polyhedron, 66, 39–42.
  • 64. Yamashita, A., Watanabe, A., Akine, S., Nabeshima, T., Nakano, M., Yamamura, T., & Kajiwara, T. (2011). Wheel-shaped ErIIIZnII3 single-molecule magnet: A macrocyclic approach to designing magnetic anisotropy. Angew. Chem. Int. Ed., 50, 4016–4019.
  • 65. Chilton, N. F. (2013). PHI User Manual v1.7.
  • 66. Clemente-Juan, J. M., Coronado, E., & Gaita-Arino, A. (2012). Magnetic polyoxometalates: from molecular magnetism to molecular spintronics and quantum computing. Chem. Soc. Rev., 41, 7464–7478.[Crossref]

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Identifiers

YADDA identifier

bwmeta1.element.-psjd-doi-10_1515_nuka-2015-0067
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