# Revealing the role of van der Waals interactions in thiophene adsorption on copper surfaces

## TL;DR

This study uses density-functional theory to investigate how van der Waals interactions influence thiophene adsorption on copper surfaces, revealing the importance of non-local dispersion forces in accurately modeling the bonding mechanism.

## Contribution

It demonstrates that including van der Waals interactions via specific functionals is crucial for correctly describing thiophene adsorption on copper, highlighting the limitations of semi-local functionals.

## Key findings

- Van der Waals interactions dominate the bonding mechanism.
- Semi-local functionals without vdW corrections can misinterpret adsorption nature.
- SCANN+rVV10 overestimates adsorption energies due to excessive orbital hybridization.

## Abstract

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 \textit{p} orbitals of S atom and the copper \textit{d}-bands and therefore overestimates the adsorption energies by an average of 16\%.