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Spatially resolved electronic and vibronic properties of single diamondoid molecules


Diamondoids are a unique form of carbon nanostructure best described as hydrogen-terminated diamond molecules1. Their diamond-cage structures and tetrahedral s p3 hybrid bonding create new possibilities for tuning electronic bandgaps, optical properties, thermal transport and mechanical strength at the nanoscale1,2. The recently discovered higher diamondoids3,4 have thus generated much excitement in regards to their potential versatility as nanoscale devices5,6,7,8,9,10,11,12,13,14,15. Despite this excitement, however, very little is known about the properties of isolated diamondoids on metal surfaces, a very relevant system for molecular electronics. For example, it is unclear how the microscopic characteristics of molecular orbitals and local electron–vibrational coupling affect electron conduction, emission and energy transfer in the diamondoids. Here, we report the first single-molecule study of tetramantane diamondoids on Au(111) using scanning tunnelling microscopy and spectroscopy. We find that the diamondoid electronic structure and electron–vibrational coupling exhibit unique and unexpected spatial correlations characterized by pronounced nodal structure across the molecular surfaces. Ab initio pseudopotential density functional calculations reveal that much of the observed electronic and vibronic properties of diamondoids are determined by surface hydrogen terminations, a feature having important implications for designing future diamondoid-based molecular devices.

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Figure 1: STM topography of tetramantane molecules.
Figure 2: STM images and DFT simulations of individual tetramantane molecules.
Figure 3: dI/dV spectroscopy of tetramantane molecules.
Figure 4: Spatial maps of the IETS intensity.

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This work was supported in part by NSF Grant Nos. DMR04-39768, EEC-0425914, COINS, UC Discovery grant ELE 05-10234, and the US Department of Energy under Contract No. DE-AC02-05CH11231. Computational resources have been provided by DOE at the National Energy Research Scientific Computing Center. Y.W. thanks the Miller Institute for a research fellowship. E.K. is a fellow of the Onassis Foundation. D.W. acknowledges support by the Alexander von Humboldt Foundation.

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Correspondence to Yayu Wang or Michael F. Crommie.

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Wang, Y., Kioupakis, E., Lu, X. et al. Spatially resolved electronic and vibronic properties of single diamondoid molecules. Nature Mater 7, 38–42 (2008).

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