Surface properties of rutile TiO2(1 1 0) from molecular dynamics and lattice dynamics at 300 K: Variable-charge model results

Geometric structure, atomic vibrations and atomic charges and their thermally induced fluctuations have been calculated as a function of depth in, and thickness of, rutile TiO2(1 1 0) slabs, within the framework of the variable-charge potential of Swamy and Gale [V. Swamy, J.D. Gale, Phys. Rev. B 62 (2000) 5406] at 300 K. Molecular dynamics simulations and lattice dynamics calculations were performed with a 2D periodic slab model for slab thicknesses between 3 and 11 triple layers (approximately 9-35 Å). Odd-even oscillations with respect to the number of slab layers are found for the surface relaxation for very thin slabs, and for the (slowly converging) rumpling in the middle of the slab. The Ti and O atomic charges in the outermost three atomic layers differ from the rest of the slab (they are less ionic); the thermal vibrations do not alter this picture. The atomic mean-square amplitudes are some 50% larger (more for O, less for Ti) at the surface than in the middle of the slab and decay rather slowly to the bulk values. Comparisons with the results of a rigid-ion potential for titania [M. Matsui, M. Akaogi, Mol. Simul. 6 (1991) 238] are presented for non-electronic properties.