Abstract

Two-photon photoemission (2PPE) spectroscopy is used to investigate the electronic structure of naphthalene dosed on Cu(1 1 1) at 86 K. The three transitions involving unoccupied orbitals were found and identified as having π ∗ molecular orbital character––the first lying 0.40 eV above the vacuum level and identified as having π ∗ b 1 u character; the second 0.30 eV below the vacuum level and having π ∗ b 3 g character; and the third lying 1.10 eV below the vacuum level with π ∗ b 2 g character. The results accord with both inverse photoemission spectroscopy (IPES) and electron transmission spectroscopy (ETS) data. There are interesting relatively unique features in the temperature programmed desorption (TPD) spectra indicative of structural reorganization of as-dosed naphthalene. Thermal processing also has a marked influence on 2PPE intensities and is taken as reflecting changes, with respect to the Cu(1 1 1) surface, of the ensemble average orientation of the naphthalene overlayer.

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