3
6
MUDRING ET AL.
of Rb Au O discussed above. Thus all the conclusions also 11. T. Leininger, A. Nicklass, W. Ku
ꢂ ꢁ
apply to Rb Au O .
ꢄ ꢁ
K
chle, H. Stoll, M. Dolg, and
A. Bergner, Chem. Phys. ¸ett. 255, 274 (1996).
2. A. Bergner, Arbeitsbericht 1990, Institut fur theoretische Chemie,
Universitat Stuttgart
3. A. Bergner, M. Dolg, W. Kuechle, H. Stoll, and H. Preuss, Mol. Phys.
0, 1431 (1993).
ꢄ
ꢃ
1
1
K
Both density functional and Hartree}Fock calculations
draw a consistent picture of the electronic structure. They
prove that Au2 is a slightly polarized Au\ anion. The
K
8
positive charge of Au1 is de"nitively smaller than expected 14. A. Savin, A. D. Becke, J. Flad, R. Nesper, H. Preuss, and H. G. von
Schnering, Angew. Chem. 103, 421 (1991); Angew. Chem. Int. Ed. Engl.
by general considerations, and is distributed within the
3
0, 409 (1991).
dumbbells over a rather wide space. This may be a further
stabilizing factor for the coexistence of gold anions and
cations in the investigated compounds.
1
5. A. Savin, O. Jepsen, J. Flad, O. K. Andersen, H. Preuss, and H. G. von
Schnering, Angew. Chem. 104, 186 (1992); Angew. Chem. Int. Ed. Engl.
3
1, 187 (1992).
6. B. Silvi and A. Savin, Nature 371, 683 (1994).
7. R. Dronskowski and P. E. Blochl, J. Phys. Chem. 97, 8617 (1993).
1
1
1
K
ACKNOWLEDGMENTS
8. M. Jansen, A.-V. Mudring, in &&Gold*Progress in Chemistry,
Biochemistry and Technology'' H. Schmidbaur, Ed., p. 745. Wiley,
Chichester, 1999.
The authors acknowledge the Fonds der Chemischen Industrie for
"
nancial support. A.-V. Mudring thanks the Studienstiftung der Hoechst 19. A. Sommer, Nature 215, 3841 (1943).
AG, the Fonds der Chemischen Industrie, the Dr. Wilhem Heinrich und 20. W. E. Spicer, A. H. Sommer, and J. G. White, Phys. Rev. 115, 57
Else Heraeus Stitfung, and the Ev. Studienwerk Villigst e.V. and its
members for support.
(1959).
21. E. Parthe
H
and B. Chabot, in &&Handbook on the Physics and Chemistry
of Rare Earth'' (K. A. Gschneider and L. Eyring, Eds.), p. 113. Elsevier,
Amsterdam, 1985.
2. M. O'Keefe and B. G. Hyde, in &&Structure and Bonding,'' Vol. 61,
p. 77. Springer-Verlag, Berlin, 1985.
REFERENCES
2
1
2
3
4
. Y. Tokura and N. Nagaosa, Science 288, 462 (2000).
. J. Dye, R. H. Huang, and D. L. Ward, J. Coord. Chem. 18, 121 (1988).
23. A Vegas, Cryst. Rev. 7, 189 (1999).
24. S. Andersson, Angew. Chem. 95, 67 (1983); Angew. Chem. Int. Ed. Engl.
22, 69 (1983).
. L. Hackspill, C. R. Hebed. Se
. G. Brauer, &&Handbuch der pra
Vol. 2, p. 395. Enke, Stuttgart, 1975.
. L. Vanino, &&Handbuch der pra
Stuttgart, 1921.
H ances Acad. Sci. 154, 209 (1912).
K
parativen anorganischen Chemie,'' 25. P. I. Kripyakevich and Yu. N. Grin, Sov. Phys. Crystallogr. 23, 45
(1978).
5
6
K
parativen. Chemie,'' Vol. 1, p. 520. Enke, 26. Yu. N. Grin, Ya. P. Yarmolyuk, and E. I. Gladyshevskii, Sov. Phys.
Crystallogr. 27, 413 (1982).
. R. W. Tank, O. Jepsen, A. Burkhardt, and O. K. Andersen, TB-LMTO- 27. C. Feldmann and M. Jansen, Z. Anorg. Allg. Chem. 621, 201 (1995).
ASA program, Version 4.7, Max-Planck-Institut fu
K
r Festko
K
rperfor- 28. C. Feldmann and M. Jansen, Angew. Chem. 105, 1107 (1993); Angew.
schung, Stuttgart, 1998.
Chem. Int. Ed. Engl. 32, 1049 (1993).
7
8
. W. Barth and L. Hedin, J. Phys. C 5, 1629 (1972).
29. C. Feldmann and M. Jansen, J. Chem. Soc. Chem. Commun. 1045
. V. R. Saunders, R. Dovesi, C. Roetti, M. Causa
R. Orlando, and C. M. Zicovich-Wilson, CRYSTAL98 User's Manual, 30. A. Pantelouris, G. Ku
University of Torino, Torino, 1998. J. Am. Chem. Soc. 117, 11,749 (1995).
. O. K. Andersen, Z. Pawlowska, and O. Jepsen, Phys. Rev. B: Condens. 31. C. Feldmann and M. Jansen, Z. Anorg. Allg. Chem. 621, 1907
Matter 34, 5253 (1986). (1995).
0. (a) D. Andrae, U. Haeussermann, M. Dolg, H. Stoll, at H. Preuss, 32. F. E. Wagner, A.-V. Mudring, and M. Jansen, unpublished. Rb Au O :
`
, N. M. Harrison,
(1994).
K
per, J. Hormes, C. Feldmann, and M. Jansen,
9
1
ꢃ
ꢄ ꢁ
¹
heoret. Chim. Acta 77, 123 (1990); (b) All pseudopotential parameters,
basis exponents, and contraction coe$cients can be found on the
IS"6.09(1) mms\ꢀ (Au(!1)), IS"3.94(1) mms\ꢀ, QS"7.24(1)
mms\ꢀ (Au(#1)); Cs Au O : IS"7.44(1) mms\ꢀ (Au(!1)), IS"
ꢃ
ꢄ ꢁ
Internet: http://www/theochem.uni-stuttgart.de.
3.33(1) mms\ꢀ, QS"6.71(1) mms\ꢀ (Au(#1)).