Zhi-Xin Hu (胡智鑫)1, Haiping Lan(蓝海平)1, 2 and Wei Ji(季威)1,
1Department of Physics and Beijing Key Laboratory of Optoelectronic Functional Materials & Micro-Nano Devices, Renmin University of China, Beijing 100872, China
2International Center for Quantum Design of functional materials, University of Science and Technology of China, Hefei, Anhui 230026, China
DOI:10.1038/srep05036 Publication Date: May 22, 2014
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.