Role of the dispersion force in modeling the interfacial properties of molecule-metal interfaces: adsorption of thiophene on copper surfaces

TL;DR

This study uses advanced density functional theory methods to analyze how dispersion forces influence the structural and energetic properties of thiophene molecules adsorbed on copper surfaces, highlighting the importance of van der Waals interactions.

Contribution

It compares different dispersion-corrected density functionals, identifying the RPBE functional as the most balanced for predicting molecule-metal interface properties.

Findings

RPBE functional provides the best balance of speed and accuracy.

Dispersion corrections significantly affect adsorption energies and geometries.

Discrepancies in adsorption sites suggest need for further experimental and theoretical work.

Abstract

We present density functional theory calculations of the geometry, adsorption energy and electronic structure of thiophene adsorbed on Cu(111), Cu(110) and Cu(100) surfaces. Our calculations employ dispersion corrections and self-consistent van der Waals density functionals (vdW-DFs). In terms of speed and accuracy, we find that the dispersion-energy-corrected Revised Perdue-Burke-Enzerhof (RPBE) functional is the "best balanced" method for predicting structural and energetic properties, while vdW-DF is also highly accurate if a proper exchange functional is used. Discrepancies between theory and experiment in molecular geometry can be solved by considering x-ray generated core-holes. However, the discrepancy concerning the adsorption site for thiophene/Cu(100) remains unresolved and requires both further experiments and deeper theoretical analysis. For all the interfaces, the PBE functional reveals a covalent bonding picture which the inclusion of dispersive contributions does not change to a vdW one. Our results provide a comprehensive understanding of the role of dispersive forces in modelling molecule-metal interfaces.