The glassy system xBi(2)O(3).(1-x)GeO2 with high bismuth content (x=0.
9) has been investigated by infrared spectroscopy in the range 200-400
0 cm(-1) and by extended X-ray absorption fine structure (EXAFS) spect
roscopy at the Ge absorption K-edge. The infrared measurements show th
at the addition of Bi2O3 to GeO2 causes a shift and splitting into two
components of the band associated with the stretching mode occurring
in the GeO4 tetrahedra. This result is accounted for by assuming that
Bi atoms perturb the environment around GeO4 units rather than change
the oxygen coordination around germanium from fourfold to sixfold. A t
etrahedral coordination for germanium atoms at all bismuth concentrati
ons is found from the EXAFS analysis. The role of the preparation proc
edure on the glass infrared transmission is discussed.