An extensive computational study of the adsorption of thiophene on transition metal surfaces: role of van der Waals

Van der Waals (vdWs) interactions play a significant role in the determination of the adsorption characteristics at the interface between a molecule and a substrate. In this study,~self-consistent inclusion of vdW interactions in density functional theory~provides a good perspective to understand the interaction between organic adsorbates and inorganic interfaces. We present the results of adsorption of thiophene (C$_{\mathrm{4}}$H$_{\mathrm{4}}$S) on various~transition metal surfaces with the goal of comparing the performance of five different vdW functionals (optB86, optB88, optPBE, revPBE, rPW86). ~Seven metallic substrates (100) are used for our study; three coinage metals (Au, Ag, Cu) and four reactive metals (Pt, Pd, Rh, Ni). The results show that vdWs inclusion enhances the interaction for Ag ( 0.08 to 0.73 eV), Au (0.14 to 0.86 eV), Cu (0.12 eV to 0.77 eV), Ni(1.56 to 2.34 eV), ~Pt (1.6 to 2.51 eV), Pd (1.67 to 2.54), Rh (1.74 to ~2.96 eV). In addition, we performed calculations for adsorption heights along with analysis of the electronic changes (charge transfer, changes in the d-band of the substrate, and change in the work function) to complement our understanding of these systems.