Theoretical insights into the surface growth of rutile TiO 2

Abstract

Adsorption of TiCl 4 molecules on the reduced [1 1 0] surface of TiO 2 is investigated using density functional theory with plane wave basis sets and pseudo-potentials. Adsorption energies and barriers are calculated and discussed. The rate of this adsorption process is calculated using transition state theory with estimated vibrational frequencies. Derived activation energies for TiCl 4 adsorption are associated with significant error bounds, which encapsulate the experimental activation energy for the overall growth process. Quantitative predictions of the rate can not be made based on these theoretical calculations alone, due to sensitive dependence on the vibrational frequencies. Building on the theoretical work presented here and previous experimental results a new kinetic model is constructed consisting of a TiCl 4 adsorption step followed by a secondary reaction with gaseous O 2. Simulations of a plug flow reactor are used to fit the kinetic constants for the rate limiting adsorption step. Unlike the previous phenomenological models, this new Eley–Rideal model is under the theoretical limit at all conditions and contains a physically motivated dependence on gas phase concentrations.