Relativistic Effects in Gold Chemistry Springer黄金化学相对论效应.pptVIP

* Valence instabilities of gold in perovskite structures The relativistic effects in gold stabilizes enormously the 6s level and destabilizes the 5d levels. As a result a variety of Au valencies from -1 to +5 are possible. Among these states the Au+2 is a special case. It is possible as an average over some gold complexes exhibiting Au-Au bonds, The formally 197Au compounds like AuO or AuCl2 are in fact Au+-Au+3 mixed valence species. The best examples of that group are Cs2Au2X6 (X=Cl, Br, I) (Wells salts). Projection of the structure of Cs2Au2X6 The crystal structure of Cs2Au2X6 may be considered as distorted perovskite structures composed of corner sharing compressed Au+X6 and elongated Au+3X6 octahedra With increasing pressure the Cs2Au2X6 structures change generally to a less distorted perovskite type. In the case of Cs2Au2I6 X-ray studies suggest an abrupt structural phase transition at 5.5 GPa to the tetragonal CsAuI3 phase (at room temperature). The 197Au M?ssbauer data show that at 4.2 K the structural transformation of Cs2Au2I6 is gradual. At 12.5 GPa (at 4 K) Au appears in only one electronic state, Au+2 . The small quadrupole splitting is an evidence of the distortion of the I6 octahedra [ S.S. Hafner, N. Kojima, J. Stanek, Li Zhang. Phys. Lett. A 192(1994)385] Conclusions The relativistic stabilization of gold 6s level and the destabilization of the 5d levels may explain not only the known unusual macroscopic properties of the metallic gold as yellow color, high density and chemical stability. This modification of the atomic level scheme leads to the interesting local electronic states of this element in compounds, which may be spectacularly investigated by 197Au M?ssbauer spectroscopy. *