Importance of dispersion in density functional calculations of cesium chloride and its related halides

Abstract

The ionic compound cesium chloride adopts a cubic crystal structure bearing the same name. However, ab initio electronic structure calculations based on density functional theory methods using generalized gradient approximation functionals do not predict that cesium chloride adopts this phase. In this paper we apply semiempirical methods (density functional theory plus a pairwise dispersion correction) to account for missing van der Waals interactions within cesium chloride. The C6 and R0 dispersion parameters for cesium are established within Grimme's DFT+D2 formalism. Inclusion of the dispersion corrections is found not only to improve the quality of structures in comparison to experiment for all cesium halides, but also leads to the correct prediction of the ground-state phase under ambient conditions.