RESUMO
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.
RESUMO
Uniaxial-stress experiments have been performed for the 3287- and 2445-cm-1 local vibrational modes assigned to the positive charge state of interstitial hydrogen [Formula: see text] and deuterium [Formula: see text], respectively, occurring in mono-crystalline rutile TiO2. The onset of the defect alignment under the stress applied perpendicular to the [001] axis is detected at 165 K (185 K), which corresponds to the activation energy of 0.53 eV (0.58 eV) for interstitial hydrogen (deuterium). Based on these findings the diffusion constants of [Formula: see text] and [Formula: see text] along the [001] axis of TiO2 are determined. The experimental data are complemented by density-functional theory calculations and compared with the earlier results on the diffusion of [Formula: see text]/[Formula: see text] at elevated temperatures up to 700 °C. It is found that the activation energy value deduced from our low-temperature stress measurements yields a very good agreement with the high-temperature data, covering a dynamic range of 12 orders of magnitude.
