The OH site in topaz: an IR spectroscopic investigation

The OH site in topaz is investigated by IR spectroscopy depending on the OH concentration and temperature. The two OH bands that can be distinguished are due to the local ordering of F and OH in opposite sites of the crystal structure. The first typical sharp band stems from OH groups with fluorine in the opposite (=acceptor) site. The second band occurs as a shoulder on the low-energy wing and is related to two opposite OH groups. The degree of local OH–OH ordering depends on the OH concentration and, due to statistical F/OH distribution, can be predicted by probability calculations. The substitution of OH for F has a non-linear effect on the increase of the lattice parameters. An autocorrelation analysis of the IR spectra revealed two temperature-induced phase transitions. At −135°C, the local symmetry changes from P1 to Pbn2₁, although this change involves only the H atoms. The transition from Pbn2₁ to Pbnm at 160°C is caused by changes of the local F/OH ordering in the crystal structure.