The optical spectra of Os4plus;lpar;5d4rpar;in single cubic crystals of K2PtCl6, Cs2ZrCl6, Cs2HfCl6, and Rb2ZrCl6at 4.2deg;K has been studied. The spectrum is characterized by very narrow lines in the region from 10 000ndash;36 000 cmminus;1. Vibrational structure is observed which may be assigned to the ungerade modes of the OsCl62minus;complex in the lattice. A crystalhyphen;field analysis within thed4manifold fits the observed ten electronic, 0sngbnd;0 transitions with an rms deviation of 228 cmminus;1for the parametersAthinsp;equals;thinsp;0, Bthinsp;equals;thinsp;741, Cthinsp;equals;thinsp;1296, Vthinsp;equals;thinsp;22490, andlgr;5dthinsp;equals;thinsp;2416cmminus;1. The calculated molar magnetic susceptibility agrees with that found for concentrated crystals such as K2OsCl6and Cs2OsCl6. The analysis of the electronic states was dependent upon a calculation of intensities for thet2g4thinsp;rarr;thinsp;t2g3egtransitions. The calculated results are given for a tetragonal distortion of the cubic field and are shown to qualitatively agree with the linewidth of the transitions. The calculatedgvalues for all observed transitions are tabulated. Finally, several conclusions about the optical spectra of5dsystems are presented.
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