ESR spectroscopy of Co<sup>2+</sup> impurities in Cd<sub>2</sub>P<sub>2</sub>S<sub>6</sub> and Cd<sub>2</sub>P<sub>2</sub>Se<sub>6</sub>
G T Long; D A Cleary; G T Long; Dept. of Chem., Washington State Univ., Pullman, WA, USA; D A Cleary; Dept. of Chem., Washington State Univ., Pullman, WA, USA
Журнал:
Journal of Physics: Condensed Matter
Дата:
1990-05-28
Аннотация:
The ESR spectra of Co<sup>2+</sup> impurities in Cd<sub>2</sub>P<sub>2</sub>S<sub>6</sub> and Cd<sub>2</sub>P<sub>2</sub>Se<sub>6</sub> are reported. The Co<sup>2+</sup> ion is an S=<sup>3</sup>/<sub>2</sub> ion and substitutes for Cd<sup>2+</sup> (S=0) ions in the Cd<sub>2</sub>P<sub>2</sub>X<sub>6</sub> crystal. The spin Hamiltonian parameters g and A were determined using an effective spin=<sup>1</sup>/<sub>2</sub>. For Cd<sub>2</sub>P<sub>2</sub>S<sub>6</sub>, g/sub ///=4.86, A/sub ///=440 MHz, g<sub>perpendicular to </sub>=4,01 and A<sub>perpendicular to </sub>=346 MHz. For Cd<sub>2</sub>P<sub>2</sub>Se<sub>6</sub>, g/sub ///=4.98, A/sub ///=565 MHz, g<sub>perpendicular to </sub>=3.85 and A<sub>perpendicular to </sub>=250 MHz. From the temperature dependence of the linewidth, the zero-field splitting, 2D, for Co<sup>2+</sup> doped into Cd<sub>2</sub>P<sub>2</sub>S<sub>6</sub> is estimated to be 127 cm<sup>-1</sup>. The individual hyperfine lines of Co<sup>2+</sup> doped into Cd<sub>2</sub>P<sub>2</sub>Se<sub>6</sub> show superhyperfine structure due to <sup>77</sup>Se(I=<sup>1</sup>/<sub>2</sub>, 7.58% natural abundance). This additional splitting is consistent with some covalent bonding between the Co<sup>2+</sup> and its six selenium ligands.
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