Coordination of water molecules with Na+ cations in a beryl channel as determined by polarized IR spectroscopy

Subtle variations of frequencies in the infrared (IR) absorption spectra of beryl have been predicted based on the coordination between extra-framework cations and water molecules in two orientations (referred to as type I and type II) trapped within the channel. In this study, the polarized IR spectra of hydrated synthetic beryl and natural beryl were measured to clarify the relationships between the frequencies of the absorption bands and the coordination states of type II water. Na⁺ was assumed to be the predominant cation coordinated to type II water in our samples, as determined by chemical analyses. These measurements revealed a clear quantitative linear relationship in absorbance between bands at 3,602 and 1,619 and at 3,589 and 1,631 cm⁻¹. On the basis of experimental and theoretical studies, we assigned these pairs of bands to the ν₁ and ν₂ modes of doubly coordinated type II H₂O and to singly coordinated type II H₂O, respectively. These assignments were supported by IR measurements of annealed natural beryl. We also conducted dehydration studies of natural beryl, in which two observed dehydration peaks, at 600 and 750°C, suggested the dehydration of type I and type II water, respectively.