Surface electronic structure. Photoelectron spectroscopies

The various forms of photoelectron spectroscopy presently available permit a straightforward determination of occupied and unoccupied surface states. The most comprehensive and authoritative collection of reviews is in the book edited by Feuerbacher et al. [44], while Ertl and Kiippers [15] also provide useful information. Here, we will only attempt to summarize how the principal versions of the technique can be used in the determination of surface electronic structure. In this context the crucial factor is that photoemission spectra represent a direct manifestation of the initial and final density of states of the emitting system. Because selection rules (matrix element effects) can be involved in the transition, the state densities may not always correspond to those derived from the band structure, but in practice there is frequently a rather close correspondence. 

The alternative approach involves the so-called photoemission yield spectroscopies, which enable empty surface states to be probed. In these, the incident photon energy is varied while the electron energies are or are not resolved. The technique can firstly be used to investigate transitions between core levels and empty states, usually by using synchrotron radiation so that sufficient photon energy is available for the excitation. Core levels have negligible dispersion in fc-space, so the measurement reveals the unoccupied conduction band and surface state transition state densities, since electrons are generated by optical transitions from a core level to either empty surface states or conduction band states. 

By using much lower energy photons, Guichar et al. [45] have developed a high sensitivity technique which probes transitions between occupied surface and bulk states and states at or above the vacuum level. 

The partial yield of electrons in an energy window AE at a fixed final state energy E, as a function of photon energy, where E is fixed at 5eV so that only secondary electrons are measured, is referred to as partial yield spectroscopy. When E 5eV, although the technique is experimentally identical, it is used to study initial state and excitonic effects and is known as constant final state spectroscopy. 

Constant initial state techniques require the photon energy and electron energy analyser to be scanned synchronously so that hv — E is kept constant. In this way, the photon energy dependent partial yield of electrons in an energy window AE at a fixed initial state energy E = E — hv is measured. Core level to empty surface state transitions are enhanced by selecting the appropriate E corresponding to a minimum in the valence band emission. 

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Recent studies using high resolution electron energy loss and photoelectron spectroscopy to investigate the effect of sulfur on the CO/Ni(100) system are consistent with an extended effect by the impurity on the adsorption and bonding of CO. Sulfur levels of a few percent of the surface nickel atom concentration were found sufficient to significantly alter the surface electronic structure as well as the CO bond strength. 

Theory and experimental methods. Since the combined experimental-theoretical approach is stressed, both the underlying theoretical and experimental aspects receive considerable attention in chapters 2 and 3. Computational methods are presented in order to introduce the nomenclature, discuss the input into the models, and the other approximations used. Thereafter, a brief survey of possible surface science experimental techniques is provided, with a critical view towards the application of these techniques to studies of conjugated polymer surfaces and interfaces. Next, some of the relevant details of the most common, and singly most useful, measurement employed in the studies of polymer surfaces and interfaces, photoelectron spectroscopy, are pointed out, to provide the reader with a familiarity of certain concepts used in data interpretation in the Examples chapter (chapter 7). Finally, the use of the output of the computational modelling in interpreting experimental electronic and chemical structural data, the combined experimental-theoretical approach, is illustrated. 

Preliminary models of the surface topography, for example, can be determined by atomic-probe methods, ion-scattering, electron diffraction, or Auger spectroscopy. The chemical bonds of adsorbates can be estimated from infrared spectroscopy. The surface electronic structure is accessible by photoelectron emission techniques. In case the surface structure is known, its electronic structure has to be computed with sophisticated methods, where existing codes more and more rely on first principles density functional theory (DFT) [16-18], or, in case of tight-binding models [19], they obtain their parameters from a fit to DFT data [20]. The fit is not without ambiguities, since it is unknown whether the density of states used for the fit is really unique. 

The most widely used technique to get information on the electronic structure of clean surfaces, nanostructures on surfaces, or even molecules adsorbed on surfaces is ultraviolet photoelectron spectroscopy (UPS). The difficulty of this method, when applying it to clusters on surfaces, is to obtain sufficient spectral contrast between the low number of adsorbed clusters and the substrate [45]. Thus, electron energy loss spectroscopy (EELS) is more successfully used as a tool for the investigation of the electronic structure of supported clusters. An interesting test case for its suitability is the characterization of supported monomers, i.e., single Cu atoms on an MgO support material [200], as this system has been studied in detail before with various surface science techniques [201-204]. The adsorption site of Cu on MgO(lOO) is predicted... 

Hudson BS and Kohler BE (1973) Polyene spectroscopy the lowest energy excited singlet state ofdiphenyloctatetraene and other linear polyenes. J Chem Phys 59 4984-5002 Hudson BS and Kohler BE (1974) Linear polyene electronic structure and spectroscopy. Ann Rev Phys Chem 25 437-460 Hudson BS and Kohler BE (1984) Electronic stmcture and spectra of finite linear polyenes. Synthetic Metals 9 241-253 Hudson BS, Ridyard JN and Diamond J (1976) Polyene spectroscopy. Photoelectron spectra of the diphenylpolyenes. J Am Chem Soc 98 1126-1129 Hudson BS, Kohler BE and Schulten K (1982) Linear polyene electronic structure and potential surfaces. In Lim EC (ed) Excited States, Vol 6, pp 1-95. Academic Press, New York Jones PF, Jones WJ and Davies B (1992) Direct observation of the 2 Ag electronic state of carotenoid molecules by consecutive two-photon absorption spectroscopy. Photochem Photohiol A Chem, 68 59-75... 

Elaborate synthetic approaches have been developed that enable significant control over the size and shape of palladium nanostructures. In order to understand the properties of the materials formed based on the preparation method, several characterization techniques have been used. These include electron microscopy, scanning probe microscopy (SPM), nuclear magnetic resonance (NMR) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, infrared (IR) spectroscopy, electrochemistry, X-ray diffraction (XRD), thermogravimetric analysis (TGA), electron diffraction, photoelectron spectroscopy, dynamic light scattering (DLS), extended X-ray absorption fine structure (EXAFS), BET surface area analysis andX-ray reflectivity (XRR). In the following section we will describe the information provided by each of these characterization techniques. 

At a surface, not only can the atomic structure differ from the bulk, but electronic energy levels are present that do not exist in the bulk band structure. These are referred to as surface states . If the states are occupied, they can easily be measured with photoelectron spectroscopy (described in section A 1.7.5.1 and section Bl.25.2). If the states are unoccupied, a teclmique such as inverse photoemission or x-ray absorption is required [22, 23]. Also, note that STM has been used to measure surface states by monitoring the tunnelling current as a fiinction of the bias voltage [24] (see section BT20). This is sometimes called scamiing tuimelling spectroscopy (STS). 

In general, several spectroscopic techniques have been applied to the study of NO, removal. X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), nuclear magnetic resonance (NMR), extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) are currently used to determine the surface composition of the catalysts, with the aim to identify the cationic active sites, as well as their coordinative environment. 

How then, can one recover some quantity that scales with the local charge on the metal atoms if their valence electrons are inherently delocalized Beyond the asymmetric lineshape of the metal 2p3/2 peak, there is also a distinct satellite structure seen in the spectra for CoP and elemental Co. From reflection electron energy loss spectroscopy (REELS), we have determined that this satellite structure originates from plasmon loss events (instead of a two-core-hole final state effect as previously thought [67,68]) in which exiting photoelectrons lose some of their energy to valence electrons of atoms near the surface of the solid [58]. The intensity of these satellite peaks (relative to the main peak) is weaker in CoP than in elemental Co. This implies that the Co atoms have fewer valence electrons in CoP than in elemental Co, that is, they are definitely cationic, notwithstanding the lack of a BE shift. For the other compounds in the MP (M = Cr, Mn, Fe) series, the satellite structure is probably too weak to be observed, but solid solutions Coi -xMxl> and CoAs i yPv do show this feature (vide infra) [60,61]. 

The adiabatic picture developed above, based on the BO approximation, is basic to our understanding of much of chemistry and molecular physics. For example, in spectroscopy the adiabatic picture is one of well-defined spectral bands, one for each electronic state. The structure of each band is then due to the shape of the molecule and the nuclear motions allowed by the potential surface. This is in general what is seen in absorption and photoelectron spectroscopy. There are, however, occasions when the picture breaks down, and non-adiabatic effects must be included to give a faithful description of a molecular system [160-163],... 

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