Theoretical Study of Electron Paramagnetic Resonance Spectra and Local Lattice Distortion for Mn²⁺ in Zn(ClO₄)₂·6(H₂O)Mg(ClO₄)₂·6(H₂O)

Abstract

The electron paramagnetic resonance (EPR) spectra of trigonal Mn²⁺ centers in Zn(ClO₄)₂·6(H₂O) and Mg(ClO₄)₂·6(H₂O) crystals were studied on the basis of the complete energy matrices for a d ⁵ configuration ion in a trigonal ligand field. It was demonstrated that the local lattice structure around a trigonal Mn²⁺ center has an compressed distortion along the crystalline c ₃ axis, and when Mn²⁺ is doped in the Zn(ClO₄)₂·6(H₂O) and Mg(ClO₄)₂·6(H₂O) crystals, there is a similar local distortion. From the EPR calculation, the local lattice structure parameters R=2.183 2 Å, for Zn(ClO₄)₂·6(H₂O), R=2.130 2 Å, for Mg(ClO₄)₂·6(H₂O) have been determined.

Keywords

Zn(ClO₄)₂·6(H₂O):Mn²⁺ / Mg(ClO₄)₂·6(H₂O):Mn²⁺ systems / local lattice structure distortion / EPR spectrum / ligand-fields theory

References

[1] Tiway C S, Skarkar R, Kumbhakar P. Synthesis and Optical Characterization of Monodispersed Mn²⁺ Doped CdS Nanoparticles[J]. Phys. Lett.A, 2008, 372(36): 5825-5830.

[2] Zajac M, Gosk J, Grzanka E, et al. Ammonothermal Synthesis of GaN Doped with Transition Metal Ions (Mn, Fe, Cr)[J]. J.Alloy Compd., 2008, 456(1-2): 324-338.

[3] Acikgoz M, Kazan S, Mikailov FA, et al. Structural Phase Transitions in Fe³⁺-Doped Ferroelectric TiGaSe₂ Crystal[J]. Solid State Commun., 2008, 145(11-12): 539-544.

[4] García-Lastra JM, Barriuso MT, Aramburu JA, et al. Anisotropic Relaxation of Mn²⁺ and Ni²⁺ Impurities in K₂MgF₄[J]. Chem. Phys. Lett., 2009, 473(1-3): 88-91.

[5] Ram K, Manju Maurya. Characterization of Mn²⁺ Doped Tetramethyl Ammonium Tetra Chlorozincate Single Crystal Using EPR and Optical Absorption[J]. Mater. Chem. Phys., 2008, 108(2-3): 257-262.

[6] Ram K, Ashutosh K Shukla. ESR and Optical Study of Mn²⁺ Doped Ammonium Selenate Single Crystals[J]. Spectrochim. Acta. Part.A, 2007, 66(2): 453-456.

[7] Ram K, Har G, Gupta SK, et al. EPR and Optical Absorption Study of Mn²⁺-Doped Zinc Ammonium Phosphate Hexahydrate Single Crystals[J]. Phys. B, 2007, 392(1-2): 92-98.

[8] Dayal R, Ramachandra D R, Putcha Venkateswarlu. Electron Paramagentic Resonance and Phase Transitions in Mn²⁺ Doped Cd(-ClO₄)₂·6H₂O[J]. J.Chem.Phys., 1979, 70(9): 2487-2490.

[9] LECH J, SLEZAK A. EPR of Mn²⁺ in [Co(H₂O)₆](ClO₄)₂ Single Crystals: Estimation of Co²⁺ Spin-Lattice Relaxation Time[J]. J.Phys.Chem. Solid, 1991, 52(5): 685-689.

[10] Prokhorov AA, Neilo GN, Prokhorov AD. EPR Studies of Phase Transitions in Perchlorates [M2+(ClO₄)₂·6H₂O] At High Pressures[J]. Phys. Solid. State, 2006, 48(2): 340-347.

[11] Akhilesh K J, Upreti GC. EPR Observation of A High Temperature Phase Transition in Zn(ClO₄)₂·6H₂O:Mn²⁺[J]. Solid State Commun., 1978, 28(7): 571-574.

[12] DAYAL R, Ramachandar Rao D. EPR Study of Phase Transitions In Single Crystals of Cd (ClO₄)₂·6H₂O And Cd (ClO₄)₂·6 D₂O[J]. Phys. Status Solidi A, 1980, 58: 155-158.

[13] Jain K, Upreti G C. EPR Study of A New Low-temperature Phase Transition in Zn(ClO₄)₂·6H₂O[J]. J. Phys. Chem. Solids, 1982, 43(6): 563-569.

[14] White A, Falk M. Phase Transitions in M(ClO₄)₂·6H₂O (M=Mg, Zn) Investigations by Adiabatic Calorimetry and Infrared Spectroscopy[J]. J. Chem. Phys., 1986, 84(6): 3484-3490.

[15] White A, Falk M. A Study of Phase Transitions In Cd(ClO₄)₂·6H₂O by Adiabatic Calorimetry and Infrared Spectroscopy[J]. J. Chem. Phys., 1985, 83(5): 2467-2474.

[16] Patel V. Temperature Evolution of The Infrared Spectrum Of Ni(-ClO₄)₂·6H₂O[J]. Solid State Commun., 1985, 53(4): 431-435.

[17] Bleaney B, Trenam RS. The Dispersion of Matter in Turbulent Flow Through A Pipe[J]. Proc. R. Soc. London, Ser. A, 1954, 223: 1-14.

[18] Kuang XY. Analysis of the Electron Paramagnetic Resonance Zero-Field Splitting for Fe³⁺ in Sapphire[J]. Phys. Rev. B, 1987, 36(1): 712-714.

[19] Newman DJ, Urban W. Interpretation of S-State Ion E.P.R. Spectra[J]. Adv. Phys., 1975, 24: 793-796.

[20] Van Vleck J H. Theory of the Variations in Paramagnetic Anisotropy Among Different Salts of the Iron Group[J]. Phys. Rev., 1932, 1: 208-210.

[21] Zhao MG, Bai GR, Jin HC. D-orbital Theory For Mn²⁺-Complex Ions in Crystals[J]. J. Phys.C, 1982, 15: 5959-5964.

[22] Lohr LL Jr. Optical Spectra of Divalent Manganese Salts. I. Energy Levels for Cubic and Lower-Symmetry Complexes[J]. J. Chem. Phys., 1966, 45(10): 3611-3622.

[23] Zheng W C. Local Trigonal Distortions of Some Paramagnetic Impurity Centers in ZnSiF₆·6H₂O Crystal[J]. Radiat. Eff. Defect Solids, 1996, 140: 329-334.

[24] Curie D, Barthon C, Canny B. Covalent Bonding of Mn²⁺ Ions in Octahedral and Tetrahedral Coordination[J]. J. Chem. Phys., 1974, 61(8): 3048-3063.

[25] Kuang XY, Zhang W. Analysis of Temperature-Dependent Electron-Paramagnetic-Rresonance Spectra for S-State Ions in MgO[J]. Phys. Rev. B, 1992, 45: 8104-8107.

[26] Jain VK. Superposition Model Analysis for The Zero-Field Splitting of Mn²⁺ in Some Crystals[J]. Modern Physics Letters B, 2006, 20: 1917-1922.