Short-range order in amphiboles

Extensive spectroscopic, diffraction and theoretical work in the last ten years has shown that short-range order (SRO) of both cations and anions is a common feature of amphiboles (Hawthorne et al. 2005). From an experimental perspective, the problem is that SRO does not obey the translational symmetry of the structure in which it occurs, and hence SRO is diffi cult to detect and decipher directly by standard diffraction methods. There is information on SRO resident in diffuse scattering from a crystal, but this information is quite diffi cult to extract, particularly when the SRO is complicated, and this approach has only been used for simpler materials. SRO can be detected by several spectroscopic techniques [e.g., infrared spectroscopy, magic-angle-spinning nuclear magnetic resonance (MAS NMR) spectroscopy], but the problem is that only part of the local arrangement is derived, and the complete picture of SRO is often not clear. Here, we examine SRO of cations and anions in monoclinic amphiboles, and show that detailed information on SRO can be derived by a combination of infrared spectroscopy and local bond-valence theory, augmented by results from Rietveld and single-crystal diffraction