对Cu(111)表面吸附的单个苉分子的分子轨道进行成像:一个实验与理论相结合的研究

结合扫描隧道显微学测量和密度泛函理论计算研究了直接吸附在Cu（111）表面的单个苉分子的电子结构性质.在低覆盖度下，苉分子表现出了单分散的吸附行为，利用dI/dV谱和图像可以辨别出吸附的单个苉分子在-1.2 V附近的最高占据态和1.6 V附近的最低未占据态.此外，还可以观测到苉分子未占据态的dI/dV信号对采谱位置具有很强的依赖性.第一性原理计算很好地模拟了这些实验结果，并且将它们归因于分子-衬底相互作用引起的苉分子不同分子轨道之间的混合态的能量和空间分布.该工作提供了吸附在金属衬底表面的苉分子的局域电子结构信息，将促进对单分子器件中电子输运性质对分子-金属电极耦合的依赖性的理解.

Imaging Molecular Orbitals of Single Picene Molecules Adsorbed on Cu(111) Surface: a Combined Experimental and Theoretical Study

Picene, which attracts the great interest of researchers, not only can be used to fabricate thin film transistors with high hole mobilities, but also is the parent material of a new type organic superconductor. Here, we investigate the electronic properties of individual picene molecules directly adsorbed on Cu(111) surface by a combination of experimental scanning tunneling microscopy/spectroscopy measurements and theoretical calculations based on the density functional theory. At low coverage, the picene molecules exhibit mono-dispersed adsorption behavior with the benzene ring planes parallel to the surface. The highest occupied state around-1.2 V and the lowest unoccupied state around 1.6 V with an obvious energy gap of the singly adsorbed picene molecule are identified by the dI/dV spectra and maps. In addition, we observe the strong dependence of the dI/dV signal of the unoccupied states on the intramolecular positions. Our first-principles calculations reproduce the above experimental results and interpret them as a specific molecule-substrate interaction and energy/spatial distributions of hybrid states mainly derived from different molecular orbitals of picene with some intermixing between them. This work provides direct information on the local electronic structure of individual picene on a metallic substrate and will facilitate the understanding the dependence of electron transport properties on the coupling between molecules and metal electrodes in single-molecule devices.