High-temperature single-crystal neutron diffraction study of natural chondrodite

The H-atom environment in a Tilly Foster chondrodite was analyzed using single-crystal neutron-diffraction data collected at 500, 700 and 900 K and previously published low temperature data collected at 10, 100 and 300 K on the same crystal (Mg_4.64Fe_0.28Mn_0.014Ti_0.023(Si_1.01O₄)₂F_1.16(OH)_0.84; Friedrich et al. in Am Mineral 86:981–989, 2001). The full mean square displacement matrix Σ of the O–H pair was determined from the temperature dependence of the anisotropic displacement parameters, enabling a proper correction of the O–H bond for thermal vibration without assumptions about the correlation of O and H movements. The results show that the perpendicular O–H motions in chondrodite are intermediate between the riding and the independent motion models. The corrected O–H bond lengths do not change with temperature whereas the corrected H···F distances show an increase of ~0.02 Å with temperature, as do the Mg–O distances. This result shows that spectroscopic observations on the strength of the covalent O–H bond cannot be interpreted unambiguously in terms of a corresponding behaviour of the associated H···O/F hydrogen bond.