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Electronic structure and EPR spectra of V 4+ in TiO 2 , SnO 2 , and GeO 2
Author(s) -
MichelCalendini F. M.,
Fichelle G.
Publication year - 1975
Publication title -
physica status solidi (b)
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.51
H-Index - 109
eISSN - 1521-3951
pISSN - 0370-1972
DOI - 10.1002/pssb.2220690236
Subject(s) - brillouin zone , linear combination of atomic orbitals , electron paramagnetic resonance , hyperfine structure , spectral line , atomic orbital , electronic structure , impurity , atomic physics , charge (physics) , crystallography , chemistry , physics , materials science , condensed matter physics , electron , nuclear magnetic resonance , quantum mechanics
The energy levels of V 4+ in a VO 6 8− complex of D 2h symmetry are computed according to an extended LCAO method with non‐orthogonal orbitals. The substitutional impurity is trapped in TiO 2 , GeO 2 , and SnO 2 lattices. The results are compared with previous calculations on these structures. The interband transitions at the centre of the Brillouin zone are related to optical data with a good approximation. A first tentative is made to explain the X‐ray spectra of TiO 2 according to the molecular diagram. The g ‐factors and the hyperfine structure constants are computed and the covalency of molecular orbitals is taken into account. The following results are obtained for g x , g y , and g z :1.917, 1.893, 1.966 for V 4+ (TiO 2 ), 1.937, 1.869, 1.953 for V 4+ (SnO 2 ) and 1.928, 1.911, 1.970 for V 4+ (GeO 2 ). The corresponding values of A x , A y , and A z in 10 −4 cm −1 units are: 35, 40, and 141 for V 4+ (TiO 2 ), 27, 40, and 148 for V 4+ (SnO 2 ), and 41, 43, and 128 for V 4+ (GeO 2 ). A comparison is made with previous works using the point charge model. The LCAO calculations give results in agreement with the values deduced from EPR experiments.