Orientation and dynamics of water molecules in beryl

TL;DR

This study uses NMR spectroscopy to investigate the orientation and motion of water molecules in beryl, revealing new insights into their orientation, hydrogen bonding, and dynamic behavior.

Contribution

It provides the first detailed analysis of water molecule orientation and dynamics in beryl, challenging previous assumptions and linking molecular motions to optical data.

Findings

Water molecules deviate 18° from the hexagonal axis.

Molecules perform librations and orientational jumps.

Librational frequencies match optical experiment results.

Abstract

Behavior of individual molecules of normal and heavy water in beryl single crystals was studied by $^1$H and $^2$H nuclear magnetic resonance spectroscopy. From temperature dependences of the spectra we deduce that type-I water molecules embedded in the beryl voids are oriented quite differently from the view established in the literature. Namely, contrary to earlier assumptions, their H-H lines deviate by about 18$^\circ$ from the hexagonal axis. We suggest that this is due to the molecules attaching to the oxygen atoms forming the beryl structural voids by a hydrogen bond. Our analysis shows that the molecules perform two types of movement: (i) rapid librations around the axis of the hydrogen bond, and (ii) less frequent orientational jumps among the twelve possible binding sites in the beryl voids. The frequencies of the librational motions are evaluated from a simple thermodynamic model, providing a good quantitative agreement with the frequencies of librations from optical experiments reported earlier.