Revisiting the (110) surface structure of TiO2:: A theoretical analysis

A detailed reexamination of the (110) surface structure of rutile TiO2 has been carried out using first-principles total-energy methods. This investigation is in response to a recent high-precision quantitative low-energy electron diffraction (LEED-IV) measurement revealing certain significant quantitative discrepancies between experiment and previous theoretical calculations. We have been able to resolve these discrepancies and achieve excellent quantitative agreement with experiment by judicious attention to reducing computational approximation errors. Our analysis also reveals that bond lengths converge much faster with slab thickness than do relaxed absolute atomic positions, which are the structural parameters typically reported in the literature for this and related systems. The effect this observation has on both the choice of slab models and the way in which surface structures should be reported for covalently bonded solids is discussed. Finally, the efficacy of freezing the lowest several atomic layers of TiO2 slab models in their bulk-like positions is examined.