Journal article
Scanning Tunneling Microscopy, Orbital-Mediated Tunneling Spectroscopy, and Ultraviolet Photoelectron Spectroscopy of Metal(II) Tetraphenylporphyrins Deposited from Vapor
Journal of the American Chemical Society, Vol.123(17), pp.4073-4080
05/02/2001
Handle:
https://hdl.handle.net/2376/106611
PMID: 11457159
Abstract
Thin films of vapor-deposited Ni(II) and Co(II) complexes of tetraphenylporphyrin (NiTPP and CoTPP) were studied supported on gold and embedded in Al−Al2O3−MTPP−Pb tunnel diodes, where M = Ni or Co. Thin films deposited onto polycrystalline gold were analyzed by ultraviolet photoelectron spectroscopy (UPS) using He I radiation. Scanning tunneling microscopy (STM) and orbital-mediated tunneling spectroscopy (STM−OMTS) were performed on submonolayer films of CoTPP and NiTPP supported on Au(111). Inelastic electron tunneling spectroscopy (IETS) and OMTS were measured in conventional tunnel diode structures. The highest occupied π molecular orbital of the porphyrin ring was seen in both STM−OMTS and UPS at about 6.4 eV below the vacuum level. The lowest unoccupied π* molecular orbital of the porphyrin ring was observed by STM−OMTS and by IETS−OMTS to be located near 3.4 eV below the vacuum level. The OMTS spectra of CoTPP had a band near 5.2 eV (below the vacuum level) that was attributed to transient oxidation of the central Co(II) ion. That is, it is due to electron OMT via the half-filled d z 2 orbital present in Co(II) of CoTPP. The NiTPP OMTS spectra show no such band, consistent with the known difficulty of oxidation of the Ni(II) ion. The STM-based OMTS allowed these two porphyrin complexes to be easily distinguished. The present work is the first report of the observation of STM−OMTS, tunnel junction OMTS, and UPS of the same compounds. Scanning tunneling microscope-based orbital-mediated tunneling provides more information than UPS or tunnel junction-based OMTS and does so with molecular-scale resolution.
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Details
- Title
- Scanning Tunneling Microscopy, Orbital-Mediated Tunneling Spectroscopy, and Ultraviolet Photoelectron Spectroscopy of Metal(II) Tetraphenylporphyrins Deposited from Vapor
- Creators
- L ScudieroDan E BarlowUrsula MazurK. W Hipps
- Publication Details
- Journal of the American Chemical Society, Vol.123(17), pp.4073-4080
- Academic Unit
- Chemistry, Department of
- Publisher
- American Chemical Society
- Identifiers
- 99900547010101842
- Language
- English
- Resource Type
- Journal article