van der Waals Corrected Density Functional Calculations of the Adsorption of Benzene on the Cu (111) Surface

被引:12
作者
Carter, Damien J. [1 ,2 ]
Rohl, Andrew L. [1 ,2 ]
机构
[1] Curtin Univ, Dept Chem, Perth, WA 6845, Australia
[2] Curtin Univ, Nanochem Res Inst, Perth, WA 6845, Australia
关键词
vdW-DF; vdW-DF2; van der Waals; copper surfaces; benzene; HOLE DIPOLE-MOMENT; METAL-SURFACES; ACCURATE DESCRIPTIONS; NONBOND INTERACTIONS; ENERGIES; CU(111); 1ST-PRINCIPLES; TRANSITION; THERMOCHEMISTRY; COMPLEXES;
D O I
10.1002/jcc.23745
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We investigate the performance of several van der Waals (vdW) functionals at calculating the interactions between benzene and the copper (111) surface, using the local orbital approach in the SIESTA code. We demonstrate the importance of using surface optimized basis sets to calculate properties of pure surfaces, including surface energies and the work function. We quantify the errors created using (3 x 3) supercells to study adsorbate interactions using much larger supercells, and show non-negligible errors in the binding energies and separation distances. We examine the eight high-symmetry orientations of benzene on the Cu (111) surface, reporting the binding energies, separation distance, and change in work function. The optimized vdW-DF(optB88-vdW) functional provides superior results to the vdW-DF(revPBE) and vdW-DF2(rPW86) functionals, and closely matches the experimental and experimentally deduced values. This work demonstrates that local orbital methods using appropriate basis sets combined with a vdW functional can model adsorption between metal surfaces and organic molecules.
引用
收藏
页码:2263 / 2271
页数:9
相关论文
共 71 条
[1]   The interaction of C6H6 and C6H12 with noble metal surfaces:: Electronic level alignment and the origin of the interface dipole -: art. no. 184109 [J].
Bagus, PS ;
Hermann, K ;
Wöll, C .
JOURNAL OF CHEMICAL PHYSICS, 2005, 123 (18)
[2]   Exchange-hole dipole moment and the dispersion interaction: High-order dispersion coefficients [J].
Becke, AD ;
Johnson, ER .
JOURNAL OF CHEMICAL PHYSICS, 2006, 124 (01)
[3]   Exchange-hole dipole moment and the ospersion interaction [J].
Becke, AD ;
Johnson, ER .
JOURNAL OF CHEMICAL PHYSICS, 2005, 122 (15)
[4]   Rings sliding on a honeycomb network: Adsorption contours, interactions, and assembly of benzene on Cu(111) [J].
Berland, K. ;
Einstein, T. L. ;
Hyldgaard, P. .
PHYSICAL REVIEW B, 2009, 80 (15)
[5]   Adsorption of benzene on copper, silver, and gold surfaces [J].
Bilic, Ante ;
Reimers, Jeffrey R. ;
Hush, Noel S. ;
Hoft, Rainer C. ;
Ford, Michael J. .
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2006, 2 (04) :1093-1105
[6]  
Boer FRd, 1988, Cohesion in Metals
[7]   CALCULATION OF SMALL MOLECULAR INTERACTIONS BY DIFFERENCES OF SEPARATE TOTAL ENERGIES - SOME PROCEDURES WITH REDUCED ERRORS [J].
BOYS, SF ;
BERNARDI, F .
MOLECULAR PHYSICS, 1970, 19 (04) :553-&
[8]   Adsorption of benzene on coinage metals:: A theoretical analysis using wavefunction-based methods [J].
Caputo, Riccarda ;
Prascher, Brian P. ;
Staemmler, Volker ;
Bagus, Paul S. ;
Woell, Christof .
JOURNAL OF PHYSICAL CHEMISTRY A, 2007, 111 (49) :12778-12784
[9]   Insight into the description of van der Waals forces for benzene adsorption on transition metal (111) surfaces [J].
Carrasco, Javier ;
Liu, Wei ;
Michaelides, Angelos ;
Tkatchenko, Alexandre .
JOURNAL OF CHEMICAL PHYSICS, 2014, 140 (08)
[10]  
Carter D. J., INPUT OUTPUT FILES V