Electron affinity levels of benzene and azabenzenes on Cu(111) and Au(110) revealed by inverse photoemission

Frank, K. H.; Dudde, R.; Koch, E. E.

doi:10.1016/0009-2614(86)80700-x

Cited by 75 publications

(35 citation statements)

References 19 publications

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“…23,24 The energy is much higher than the onset of ϳ2.4 eV observed in the current experiment. The idea is supported by the observation using the inverse photoemission spectroscopy and two-photon photoemission spectroscopy of the benzene molecule adsorbed on the Cu͑111͒ surface and the e 2u state is assigned at ϳ4.6 eV above the Fermi level.…”

Section: Resultscontrasting

confidence: 61%

Local chemical reaction of benzene on Cu(110) via STM-induced excitation

Komeda

Kim

Fujita

et al. 2004

The Journal of Chemical Physics

103

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We have investigated the mechanism of the chemical reaction of the benzene molecule adsorbed on Cu(110) surface induced by the injection of tunneling electrons using scanning tunneling microscopy (STM). With the dosing of tunneling electrons of the energy 2-5 eV from the STM tip to the molecule, we have detected the increase of the height of the benzene molecule by 40% in the STM image and the appearance of the vibration feature of the nu(C-H) mode in the inelastic tunneling spectroscopy (IETS) spectrum. It can be understood with a model in which the dissociation of C-H bonds occurs in a benzene molecule that induces a bonding geometry change from flat-lying to up-right configuration, which follows the story of the report of Lauhon and Ho on the STM-induced change of benzene on the Cu(100) surface. [L. J. Lauhon and W. Ho, J. Phys. Chem. A 104, 2463 (2000)]. The reaction probability shows a sharp rise at the sample bias voltage at 2.4 V, which saturates at 3.0 V, which is followed by another sharp rise at the voltage of 4.3 V. No increase of the reaction yield is observed for the negative sample voltage up to 5 eV. In the case of a fully deuterated benzene molecule, it shows the onset at the same energy of 2.4 eV, but the reaction probability is 10(3) smaller than the case of the normal benzene molecule. We propose a model in which the dehydrogenation of the benzene molecule is induced by the formation of the temporal negative ion due to the trapping of the electrons at the unoccupied resonant states formed by the pi orbitals. The existence of the resonant level close to the Fermi level ( approximately 2.4 eV) and multiple levels in less than approximately 5 eV from the Fermi level, indicates a fairly strong interaction of the Cu-pi(*) state of the benzene molecule. We estimated that the large isotope effect of approximately 10(3) can be accounted for with the Menzel-Gomer-Redhead (MGR) model with an assumption of a shallow potential curve for the excited state.

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Section: Resultscontrasting

confidence: 61%

Local chemical reaction of benzene on Cu(110) via STM-induced excitation

Komeda

Kim

Fujita

et al. 2004

The Journal of Chemical Physics

103

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“…[32] The result indicates that the transition energy agrees well with the experimental observations, but the energy is larger for gold than for silver, as observed in inverse photon electron spectroscopic measurements. [66,67] For pyridine interacting with bimetallic clusters, the present result indicates that a similar phenomenon takes place. The transition energies increase with increasing gold composition, as listed in Table 7.…”

Section: Vibrational Raman Spectra Of Pyàau M Ag Nsupporting

confidence: 62%

Binding Interactions and Raman Spectral Properties of Pyridine Interacting with Bimetallic Silver–Gold Clusters

Ren

Zhang

2006

ChemPhysChem

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The binding interactions between pyridine and bimetallic silver-gold clusters are investigated using density functional theory (DFT). The binding energies of pyridine-bimetallic cluster complexes indicate that the bonding depends strongly on the binding site (Au or Ag atom) and bonding molecular orbitals in a given configuration. The donation of the lone-pair electrons of the nitrogen of pyridine to an appropriate unoccupied orbital of each metal cluster plays an important role. The low-lying excited states and charge-transfer states of four stable complexes of interest are calculated on the basis of a time-dependent DFT method. In nonresonance Raman scattering processes, the influence of binding interactions on the relative Raman intensity of totally symmetric pyridine vibrational modes is discussed. These calculated relative Raman intensities are compared with observed surface-enhanced Raman spectra of pyridine adsorbed on silver-gold alloy surfaces.

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“…We also note that inverse photoemission results show that the adsorption of pyridine on the Au͑110͒ (1 ϫ 2) surface in vacuum quenches the surface state located close to the Fermi energy of Au. 21 The feature associated with the subsurface states on Au͑110͒ at ϳ3.5 eV can still be identified on the pyridine/Au͑110͒ surface but is shifted slightly to lower energy ͑Fig. 1a͒.…”

Section: Resultsmentioning

confidence: 96%

Adsorption of Pyridine on Au(110) as Measured by Reflection Anisotropy Spectroscopy

Maunder

Lucas

et al. 2003

J. Electrochem. Soc.

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The reflection anisotropy spectra of pyridine adsorbed onto a Au͑110͒ surface in an electrochemical cell demonstrates that this system forms an ordered structure. The reflection anisotropy spectroscopy ͑RAS͒ of pyridine/Au͑110͒ is attributed to n Ϫ * transitions which are shifted from their position in gas-phase spectra by the effects of the interaction of the N lone pair orbitals with the Au͑110͒ surface. The time dependence of the reflection anisotropy spectrum of the pyridine/Au͑110͒ system shows that after the initial onset of pyridine adsorption it takes ϳ5 min for the system to yield the spectrum of the equilibrium ordered structure. A similar time is required for the RAS signal to return to that of the Au͑110͒ surface following the desorption of pyridine.

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Electron affinity levels of benzene and azabenzenes on Cu(111) and Au(110) revealed by inverse photoemission

Cited by 75 publications

References 19 publications

Local chemical reaction of benzene on Cu(110) via STM-induced excitation

Local chemical reaction of benzene on Cu(110) via STM-induced excitation

Binding Interactions and Raman Spectral Properties of Pyridine Interacting with Bimetallic Silver–Gold Clusters

Adsorption of Pyridine on Au(110) as Measured by Reflection Anisotropy Spectroscopy

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