Benzene adsorbed on metals: Concerted effect of covalency and van der Waals bonding

被引:255
作者
Liu, Wei [1 ]
Carrasco, Javier [2 ]
Santra, Biswajit [1 ,3 ]
Michaelides, Angelos [4 ,5 ]
Scheffler, Matthias [1 ]
Tkatchenko, Alexandre [1 ]
机构
[1] Max Planck Gesell, Fritz Haber Inst, D-14195 Berlin, Germany
[2] CSIC, Inst Catalisis & Petroleoquim, E-28049 Madrid, Spain
[3] Princeton Univ, Dept Chem, Princeton, NJ 08544 USA
[4] UCL, London Ctr Nanotechnol, Thomas Young Ctr, London WC1E 6BT, England
[5] UCL, Dept Chem, London WC1E 6BT, England
基金
欧洲研究理事会;
关键词
ADSORPTION; SURFACES; PT(111); 1ST-PRINCIPLES; MOLECULE; PD(111); HEAT;
D O I
10.1103/PhysRevB.86.245405
中图分类号
T [工业技术];
学科分类号
08 ;
摘要
The adsorption of aromatic molecules on metal surfaces plays a key role in condensed matter physics and functional materials. Depending on the strength of the interaction between the molecule and the surface, the binding is typically classified as either physisorption or chemisorption. Van der Waals (vdW) interactions contribute significantly to the binding in physisorbed systems, but the role of the vdW energy in chemisorbed systems remains unclear. Here we study the interaction of benzene with the (111) surface of transition metals, ranging from weak adsorption (Ag and Au) to strong adsorption (Pt, Pd, Ir, and Rh). When vdW interactions are accurately accounted for, the barrier to adsorption predicted by standard density-functional theory (DFT) calculations essentially vanishes, producing a metastable precursor state on Pt and Ir surfaces. Notably, vdW forces contribute more to the binding of covalently bonded benzene than they do when benzene is physisorbed. Comparison to experimental data demonstrates that some of the recently developed methods for including vdW interactions in DFT allow quantitative treatment of both weakly and strongly adsorbed aromatic molecules on metal surfaces, extending the already excellent performance found for molecules in the gas phase.
引用
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页数:6
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