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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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