Atomistic simulation of topaz: Structure, defect, and vibrational properties

The clay force field (CLAYFF) was supplemented by fluorine potential parameters deriving from experimental structures and used to model various topazes. The calculated cell parameters agree well with the observed structures. The quasi-linear correlation of the b lattice parameter to different F/OH ratios calculated by changing fluorine contents in OH-topaz supports that the F content can be measured by an optical method. Hydrogen bond calculations reveal that the hydrogen bond interaction to H1 is stronger than that to H2, and the more fluorine in the structure, the stronger the hydrogen bond interaction of hydroxyl hydrogen. Defect calculations provide the formation energies of all common defects and can be used to judge the ease of formation of them. The calculated vibrational frequencies are fairly consistent with available experimental results, and the 1080-cm⁻¹ frequency often occurring in natural OH-topaz samples can be attributed to Si–F stretching because of the F substitution to OH and the Al–Si exchange. (paper)