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Abstract
Key events and concepts in the development of tunneling spectroscopy, especially in the context of the scanning tunneling microscope, are reviewed. Focus is placed on the single-molecule spectroscopy of adsorbates on surfaces. Examples of molecular images with sub-molecular resolution are provided. Molecular electronic spectra obtained in the STM are displayed and contrasted with results from techniques requiring large (>109) numbers of molecules. Correlation between the nanoscale method of orbital-mediated tunneling spectroscopy (OMTS) and the microscale methods of ultraviolet photoelectron spectra (UPS) and electrochemical oxidation and reduction potentials will be made. Mapping of electron-transport paths through a molecule as a function of electron energy will be demonstrated. Specific examples of STM based OMTS will be drawn from porphyrins and phthalocyanines on Au(111).
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