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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 32, Number 6
BKCSDE 32(6)
June 20, 2011 

Temperature and Coverage Dependent Quasi-reversible Two-photon Photoemission of 1-phenyl-1-propyne on Cu(111)
Youngku Sohn*, Wei Wei, Weixin Huang, John M. White
Two-photon photoemission spectroscopy, Image potential state, Surface state, Photoexcitation charge transfer, 1-Phenyl-1-propyne (PP)
A temperature- and coverage-dependant quasi-reversible change in two-photon photoemission (2PPE) of chemisorbed 1-phenyl-1-propyne (PP) on Cu(111) is reported. For PP on Cu(111) at 300 K probed at a photon energy of 4.13 eV, two broad peaks of comparable intensity show final state energies of 7.25 and 7.75 eV above the Fermi level. The former peak could be assigned to the first image potential state (IS, n = 1) and/or unoccupied molecular orbital (UMO), located at 3.1 eV above the Fermi level. The latter is plausibly attributed to a mix of unoccupied higher-order IS (and/or UMO) and occupied surface state (SS) of Cu(111). With decreasing the temperature, the former 2PPE peak shows a shift in position by about 0.2 eV, and the latter exhibits a dramatic increase in intensity. In the system, intermolecular interactions (and/or order-disorder transition) of PP and substrate lattice temperature may play a significant role in change in photoexcitation lifetime (or excitation cross-section), and the unoccupied molecular orbital (UMO)-metal (IS) charge transfer coupling. Our unique 2PPE results provide a deeper insight for understanding photoexcitation charge transfer with temperature in an organic molecule/metal system.
1980 - 1984
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