Threefold coordinated germanium in a GeO2 melt
Songming Wan, Shujie Zhang, Bin Li, Xue Zhang, Xiaoye Gong, Jinglin You
Abstract
Abstract The local structure around germanium is a fundamental issue in material science and geochemistry. In the prevailing viewpoint, germanium in GeO 2 melt is coordinated by at least four oxygen atoms. However, the viewpoint has been debated for decades due to several unexplained bands present in the GeO 2 melt Raman spectra. Using in situ Raman spectroscopy and density functional theory (DFT) computation, we have found a [GeOØ 2 ] n (Ø = bridging oxygen) chain structure in a GeO 2 melt. In this structure, the germanium atom is coordinated by three oxygen atoms and interacts weakly with two neighbouring non-bridging oxygen atoms. The bonding nature of the chain has been analyzed on the basis of the computational electronic structure. The results may settle down the longstanding debate on the GeO 2 melt structure and modify our view on germanate chemistry.