Reorientation kinetics of hydroxyl groups in anatase TiO2

J Chem Phys. 2018 Jul 28;149(4):044507. doi: 10.1063/1.5039584.

Abstract

The reorientation kinetics of hydrogen in a variety of complexes in the anatase polymorph of TiO2 was investigated by means of stress-induced dichroism. For the hydrogen-defect resulting in an O-H vibrational mode with a frequency of 3389 cm-1, the energy barrier separating adjacent equivalent in-plane sites of hydrogen was determined to be independent of the isotope and equal to 0.74 ± 0.02 eV, whereas the attempt frequency was found to be (1.10 ± 0.20) × 1012 and (0.75 ± 0.15) × 1012 s-1 for hydrogen and deuterium, respectively. The defect with vibrational modes at 3412 and 3417 cm-1 previously assigned to isolated hydrogen did not reveal alignment under the stress up to room temperature, which indicates that the barrier of hydrogen motion is above 0.9 eV.