X-ray electron density investigation of chemical bonding in van der Waals materials

Van der Waals (vdW) solids have attracted great attention ever since the discovery of graphene, with the essential feature being the weak chemical bonding across the vdW gap. The nature of these weak interactions is decisive for many extraordinary properties, but it is a strong challenge for current theory to accurately model long-range electron correlations. Here we use synchrotron X-ray diffraction data to precisely determine the electron density in the archetypal vdW solid, TiS 2 , and compare the results with density functional theory calculations. Quantitative agreement is observed for the chemical bonding description in the covalent TiS 2 slabs, but significant differences are identified for the interactions across the gap, with experiment revealing more electron deformation than theory. The present data provide an experimental benchmark for testing theoretical models of weak chemical bonding. Electron density in TiS 2 is determined by synchrotron X-ray diffraction, which reveals significant differences between experimental data and theory for interlayer van der Waals interactions.