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Electron-spin-resonance study of Tl atom defects in KCl and relativistic many-body analysis of the hyperfine structure

1981; American Physical Society; Volume: 24; Issue: 1 Linguagem: Inglês

10.1103/physrevb.24.29

1095-3795

E. Goovaerts, J. Andriessen, S. V. Nistor, D. Schoemaker,

Advanced Chemical Physics Studies

Two thallium atom defects of tetragonal symmetry around $〈100〉$ are produced by x irradiation above 230 K in KCl: TlCl. Their electron-spin-resonance spectra are characterized by comparable and large $g$ shifts but quite different hyperfine parameters. A relativistic many-body calculation of the ${\mathrm{Tl}}^{0}$ atom hyperfine interaction including the effect of a tetragonal crystal field permits a quantitative analysis of the spin-Hamiltonian parameters. It is found in particular that the hyperfine data of the two ${\mathrm{Tl}}^{0}$ defects can be explained by assuming the presence of one or two perturbing positive charges, respectively, and a corresponding 35 and 45% delocalization of the $6{p}^{1}$ electron on the surrounding lattice. This analysis together with x-ray production, optical-excitation, and pulse-anneal data and the fact that both ${\mathrm{Tl}}^{0}$ defects can only be produced at temperatures where negative-ion vacancies are mobile (>230 K) allows one to propose precise defect structures: In one defect the ${\mathrm{Tl}}^{0}$ atom (on a positive-ion site) is associated with a single negative-ion vacancy in a nearest-neighbor position along $〈100〉$; in the other one, the ${\mathrm{Tl}}^{0}$ is flanked by two nearest-neighbor negative-ion vacancies along $〈100〉$. The data also provide strong evidence for the existence of a defect consisting of a ${\mathrm{Tl}}^{+}$ ion and a nearest-neighbor anion vacancy.