Pair distribution function analysis driven by atomistic simulations: Application to microwave radiation synthesized TiO$_2$ and ZrO$_2$

Abstract

A workflow is presented for performing pair distribution function (PDF) analysis of defected materials using structures generated from atomistic simulations. A large collection of structures, which differ in the types and concentrations of defects present, are obtained through energy minimization with an empirical interatomic potential. Each of the structures is refined against an experimental PDF. The structures with the lowest goodness of fit Rw values are taken as being representative of the experimental structure. The workflow is applied to anatase titanium dioxide (a-TiO2) and tetragonal zirconium dioxide (t-ZrO2) synthesized in the presence of microwave radiation, a low temperature process that generates disorder. The results suggest that titanium vacancies and interstitials are the dominant defects in a-TiO2, while oxygen vacancies dominate in t-ZrO2. Analysis of the atomic displacement parameters extracted from the PDF refinement and mean squared displacements calculated from molecular dynamics simulations indicate that while these two quantities are closely related, it is challenging to make quantitative comparisons between them. The workflow can be applied to other materials systems, including nanoparticles.