Many-Body Dispersion Correction Effects on Bulk and Surface Properties of Rutile and Anatase TiO$_2$

Abstract

Titanium dioxide (titania, TiO$_2$) is a widely studied material with diverse applications. Here, we explore how pairwise and many-body descriptions of van der Waals dispersion interactions perform in atomistic modeling of the two most important TiO$_2$ polymorphs, rutile and anatase. In particular, we obtain an excellent description of both bulk structures from density-functional theory (DFT) computations with the many-body dispersion (MBD) method of Tkatchenko and co-workers coupled to an iterative Hirshfeld partitioning scheme ("Hirshfeld-I"). Beyond the bulk, we investigate the most important crystal surfaces, namely, rutile (110), (101), and (100) and anatase (101), (100), and (001). Dispersion has a highly anisotropic effect on the different ($\textit{hkl}$) surfaces; this directly changes the predicted nanocrystal morphology as determined from Wulff constructions. The periodic DFT+MBD method combined with Hirshfeld-I partitioning appears to be promising for future large-scale atomistic studies of this technologically important material.V.L.D. gratefully acknowledges a postdoctoral fellowship from the Alexander von Humboldt Foundation. This work used the ARCHER UK National Supercomputing Service, access to which was granted via support for the UKCP consortium (Engineering and Physical Sciences Research Council Grant EP/K014560/1)