2019/07/23 by Abhirup Patra, Adrienn Ruzsinszky, Patra, Abhirup +1
Physics and Astronomy · #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Materials Science (cond-mat.mtrl-sci) #cond-mat.mtrl-sci #physics.chem-ph
paper · pdf · doi:10.48550/arxiv.1907.10028
arxiv created 2019/07/23 · arxiv updated 2019/07/24
Accurate modeling of electronic and structural properties of organic molecule-metal interfaces are challenging problems because of the complicated electronic distribution of molecule and screening of charges at the metallic surface. This is also the reason why the organic/inorganic system can be engineered for several applications by fine-tuning the metallic work function. Here, we use density-functional theory (DFT) calculations with different level of functional approximations for a systematic study of thiophene interacting with Copper surfaces. In particular, we considered adsorbed structures with the thiophene molecule seated on the top site, with the S atom of the molecule located on the top of a Cu atom. In this work, we find that the weak chemisorption hypothesis of thiophene binding on the copper surface is well justified by the two meta-GGAs-based approximations, SCAN and SCAN+rVV10. PBE-GGA and TM meta-GGA describe it as a physisorption phenomenon by significantly underestimating the adsorption energies. Calculated adsorption energy curves reveal that non-local dispersion interaction between the molecule and metallic surface predominantly controls the bonding mechanism and thus, modifies the copper's work function. Our results imply that semi-local functionals without any kind of van der Waals (vdW) correction can often misinterpret this as physisorption, while, a fortuitous error cancellation can give a right description of this adsorption picture for a wrong reason as in the case of SCAN. The calculated density of states of the adsorbed molecule shows that the long-range vdW correction of SCAN+rVV10 causes more than enough hybridization between the p orbitals of S atom and the copper d-bands and therefore overestimates the adsorption energies by an average of 16%.