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EPR and Optical Absorption Study of Cr3+-Doped Dipotassium Tetrachloropalladate

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Abstract

X-band electron paramagnetic resonance (EPR) study of Cr3+-doped dipotassium tetrachloropalladate single crystal is done at liquid nitrogen temperature. EPR spectrum shows two sites. The spin-Hamiltonian parameters have been evaluated by employing hyperfine resonance lines observed in EPR spectra for different orientations of crystal in externally applied magnetic field. The values of spin-Hamiltonian and zero-field splitting (ZFS) parameters of Cr3+ ion-doped DTP for site I are: g x  = 2.096 ± 0.002, g y  = 2.167 ± 0.002, g z  = 2.220 ± 0.002, D = (89 ± 2) × 10−4 cm−1, E = (16 ± 2) × 10−4 cm−1. EPR study indicates that Cr3+ ion enters the host lattice substitutionally replacing K+ ion and local site symmetry reduces to orthorhombic. Optical absorption spectra are recorded at room temperature. From the optical absorption study, the Racah parameters (B = 521 cm−1, C = 2,861 cm−1), cubic crystal field splitting parameter (Dq = 1,851 cm−1) and nephelauxetic parameters (h = 2.06, k = 0.21) are determined. These parameters together with EPR data are used to discuss the nature of bonding in the crystal.

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Acknowledgments

We are grateful to the Head, SAIF, I.I.T. Mumbai, Powai, Mumbai for providing the facility of EPR spectrometer. One of the authors, Shri Devi Pandey, is grateful to the Head, Department of Physics, University of Allahabad, Allahabad for providing departmental facilities.

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Authors and Affiliations

  1. EPR Laboratory, Department of Physics, University of Allahabad, Allahabad, 211002, India

    Ram Kripal & Shri Devi Pandey

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  1. Ram Kripal
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  2. Shri Devi Pandey
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Correspondence to Ram Kripal.

Appendix

Appendix

Angular variation of the field position EPR fine structure lines for orthorhombic spin Hamiltonian.

(i) For xy-plane

M = 3/2↔1/2

$$B = B_{ 0} + [D{ - 3}E ( 2 {\text{Cos}}^{ 2} \theta - 1 ) ]-\left( {\frac{ 2 4}{{{\text{B}}_{ 0} }}} \right)E^{2} {\text{Sin}}^{2} \theta \;{\text{Cos}}^{2} \theta$$

M = 1/2↔−1/2

$$B = B_{ 0} + \left( {\frac{3}{{4B_{0} }}} \right) [D- 3E ( 2 {\text{Cos}}^{ 2} \theta - 1 ) ]+ \left( {\frac{ 2 4}{{{\text{B}}_{ 0} }}} \right)E^{2} {\text{Sin}}^{2} \theta \;{\text{Cos}}^{2} \theta$$

M = −1/2↔−3/2

$${\text{B}} = {\text{B}}_{ 0} - [ {\text{D - 3E(2Cos}}^{ 2} \theta { - 1)] - }\left( {\frac{ 2 4}{{{\text{B}}_{ 0} }}} \right)E^{2} {\rm Sin}^{2} \theta {\rm Cos}^{2} \theta$$

(ii) For yz-plane

M = 3/2↔1/2

$$B = B_{ 0} - [D ( 3 {\text{Cos}}^{ 2} \theta - 1 )- 3E ( 1-{\text{Cos}}^{ 2} \theta ) ]-\left( {\frac{ 6}{{B_{ 0} }}} \right)(D + E)^{2} {\text{Sin}}^{2} \theta \;{\text{Cos}}^{2} \theta$$

M = 1/2↔−1/2

$$B = B_{ 0} + \left( {\frac{ 3}{{ 4 {\text{B}}_{ 0} }}} \right) [D\;{\text{Sin}}^{2} \theta -E ( 1+ {\text{Cos}}^{ 2} \theta ) ]+ \left( {\frac{ 6}{{B_{ 0} }}} \right)(D + E)^{2} {\text{Sin}}^{2} \theta \;{\text{Cos}}^{2} \theta$$

M = −1/2↔−3/2

$$B = B_{ 0} + [D ( 3 {\text{Cos}}^{ 2} \theta - 1 ) { - 3}E ( 1-{\text{Cos}}^{ 2} \theta ) ]-\left( {\frac{ 6}{{B_{ 0} }}} \right)(D + E)^{2} {\text{Sin}}^{2} \theta \;{\text{Cos}}^{2} \theta$$

(iii) For zx-plane

M = 3/2↔1/2

$$B = B_{ 0} - [D ( 3 {\text{Cos}}^{ 2} \theta - 1 )+ 3E ( 1-{\text{Cos}}^{ 2} \theta ) ]-\left( {\frac{ 6}{{B_{ 0} }}} \right)(D - E)^{2} {\text{Sin}}^{2} \theta \;{\text{Cos}}^{2} \theta$$

M = 1/2↔-1/2

$$B = B_{ 0} - \left( {\frac{ 3}{{ 4B_{ 0} }}} \right) [D\;{\text{Sin}}^{2} \theta + E ( 1+ {\text{Cos}}^{ 2} \theta ) ]-\left( {\frac{ 6}{{{\text{B}}_{ 0} }}} \right)(D - E)^{2} {\text{Sin}}^{2} \theta \;{\text{Cos}}^{2} \theta$$

M = −3/2↔−1/2

$$B = B_{ 0} + [D ( 3\;{\text{Cos}}^{ 2} \theta - 1 )+ 3E ( 1-{\text{Cos}}^{ 2} \theta ) ]-\left( {\frac{ 6}{{B_{ 0} }}} \right)(D - E)^{2} {\text{Sin}}^{2} \theta \;{\text{Cos}}^{2} \theta$$

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Kripal, R., Pandey, S.D. EPR and Optical Absorption Study of Cr3+-Doped Dipotassium Tetrachloropalladate. Appl Magn Reson 45, 731–742 (2014). https://doi.org/10.1007/s00723-014-0550-6

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