A momentum space view of the surface chemical bond

被引:25
作者
Berkebile, Stephen [1 ]
Ules, Thomas [1 ]
Puschnig, Peter [2 ]
Romaner, Lorenz [2 ]
Koller, Georg [1 ]
Fleming, Alexander J. [1 ]
Emtsev, Konstantin
Seyller, Thomas [3 ]
Ambrosch-Draxl, Claudia [2 ]
Netzera, Falko P. [1 ]
Ramsey, Michael G. [1 ]
机构
[1] Karl Franzens Univ Graz, A-8010 Graz, Austria
[2] Univ Leoben, Leoben, Austria
[3] Univ Erlangen Nurnberg, Erlangen, Germany
关键词
METAL-SURFACES; CHEMISORPTION; PHOTOEMISSION; SEXIPHENYL; ELECTROLUMINESCENCE; ORIENTATION; DISPERSION; AU(111); CU(111); FILM;
D O I
10.1039/c0cp01458c
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Well-ordered and oriented monolayers of conjugated organic molecules can offer new perspectives on surface bonding. We will demonstrate the importance of the momentum distribution, or symmetry, of the adsorbate molecules' p orbitals in relation to the states available for hybridization at the metal surface. Here, the electronic band structure of the first monolayer of sexiphenyl on Cu(110) has been examined in detail with angle-resolved ultraviolet photoemission spectroscopy over a large momentum range and will be compared to measurements of a multilayer thin film and to density functional calculations. In the monolayer, the one-dimensional intramolecular band structure can still be recognized, allowing an accurate determination of orbital modification upon bonding and the relative energetic positions of the electronic levels. It is seen that the character of the molecular p orbitals is largely maintained despite strong mixing between Cu and molecular states and that the lowest unoccupied molecular orbital (LUMO) is filled by hybridization with Cu s,p states rather than through a charge transfer process. It is also shown that the momentum distribution of the substrate states involved and the periodicity of the molecular overlayer play a large role in the final E(k) distribution of the hybrid states. The distinct momentum distribution of the LUMO, interacting with the Cu substrate s, p valence bands around the gap in the surface projection of the bulk band structure, make this system a particularly illustrative example of momentum resolved hybridization. This system demonstrates that, for hybridization to occur, not only do states require overlap in energy and space, but also in momentum.
引用
收藏
页码:3604 / 3611
页数:8
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