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Ground and Excited Electronic Energy Surfaces of the MnS4 Cluster in ZnS:Mn2+

Published online by Cambridge University Press:  26 February 2011

J. W. Richardson  and
G. J. H. Janssen
J. W. Richardson
Affiliation:
Purdue University, Dept. of Chemistry, West Lafayette, IN 47907
G. J. H. Janssen
Affiliation:
University of Groningen, Laboratory of Chemical Physics, Department of Chemistry, Groningen, The Netherlands
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Abstract

Gaussian-based Self Consistent Field (SCF) MOs are obtained at various nuclear geometries for the MnS4 cluster in the external potential of cubic ZnS. Electronic relaxation and d-shell electron correlation effects are then included. For Td symmetry, quartet d-d excitation energies calculated as functions of R(Mn-S) qualitatively resemble the simple CF diagram. While separations between successive quartet levels agree closely with experiment, the threshold is about 0.5 eV high; much of this discrepancy is removed by including additional correlation effects from charge-transfer states. Large Jahn-Teller (JT) splittings of 4T1 and 4T2 levels are found with D2d distortion. Difficulty in accurately evaluating force constants interferes with predicting the corresponding deformations and stabilization energies. Estimates, encorporating the observed Stokes'; shift and JT stabilization energy, are that R(Mn-S) decreases by ∼0.1 Å and the S-Mn-S dihedral angle increases by 7sim;8°, in the lowest quartet level.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 89: Symposium Q – Diluted Magnetic (Semimagnetic) Semiconductors , 1986 , 203
Copyright
Copyright © Materials Research Society 1987

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References

1. See, for example, Orgel, L.E., J. Chem. Phys. 23, 1004 (1955), for the basic crystal field picture.Google Scholar
2. Curie, D., Barthou, C., and Canny, B., J. Chem. Phys. 61, 3048 (1974).CrossRefGoogle Scholar
3. Fazzio, A., Caldas, M.J., and Zunger, A., Phys. Rev. B 30, 3430 (1984).Google Scholar
4. McClure, D.S., J. Chem. Phys. 39, 2850 (1963).Google Scholar
5. Parrot, R., Naud, C., Porte, C., Fournier, D., Boccara, A.C., and Rivoal, J.C., Phys. Rev. B 17, 1057 (1978).Google Scholar
6. Langer, D.W. and Ibuki, S., Phys. Rev. 138, A809 (1965).Google Scholar
7. Gumlich, H.E., Pfrogner, R.L., Shaffer, J.C., and Williams, F.E., J. Chem. Phys. 44, 3929 (1966).CrossRefGoogle Scholar
8. Goede, O. and Thong, D.D., Phys. Stat. Solidi (b) 124, 343 (1984).CrossRefGoogle Scholar
9. Liehr, A.D., J. Phys. Chem. 67, 389 (1963) gives all vibronic coupling constants through third order.CrossRefGoogle Scholar
10. Wachters, A.J.H., J. Chem. Phys. 52, 1033 (1970).Google Scholar
11. Hay, P.J., J. Chem. Phys. 66, 4377 (1977).Google Scholar
12. Roos, B. and Siegbahn, P., Theor. Chim. Acta 17, 209 (1970).Google Scholar
13. Pueyo, L. and Richardson, J.W., J. Chem. Phys. 67, 3577 (1977). Note that the CEC correction makes use of the differences between the empirical and theoretical SCF sextet-quartet excitation energies of the free Mn2+ ion.Google Scholar
14. Ves, S., Strössner, K., Gebhardt, W., and Cardonna, M., Solid State Comm. 57, 335 (1986).Google Scholar
15. Janssen, G.J.M., Doctoral Thesis, University of Groningen, 1986.Google Scholar
16. Mehra, A., J. Electrochem. Soc. 118, 136 (1971).CrossRefGoogle Scholar