Photoemission direct

Angle between the photoemission direction and the incident X-ray direction Degree of surface coverage Inelastic mean free path... 

When the double-layer thickness does not exceed the de Broglie wavelength of the emitted electron and in the absence of specifically adsorbed ions and organic adsorbates, the interfacial structure has little influence on photoemission directly. In other words, the double layer in concentrated electrolytes is transparent and the electrons can tunnel through the inner and outer (diffuse) layers. Experimentally, variation of the electrolyte concentration using an uncharged scavenger (N2O) permits two effects to be resolved. At... 

Femtosecond lasers represent the state-of-the-art in laser teclmology. These lasers can have pulse widths of the order of 100 fm s. This is the same time scale as many processes that occur on surfaces, such as desorption or diffusion. Thus, femtosecond lasers can be used to directly measure surface dynamics tlirough teclmiques such as two-photon photoemission [85]. Femtochemistry occurs when the laser imparts energy over an extremely short time period so as to directly induce a surface chemical reaction [86]. 

The dynamics of fast processes such as electron and energy transfers and vibrational and electronic deexcitations can be probed by using short-pulsed lasers. The experimental developments that have made possible the direct probing of molecular dissociation steps and other ultrafast processes in real time (in the femtosecond time range) have, in a few cases, been extended to the study of surface phenomena. For instance, two-photon photoemission has been used to study the dynamics of electrons at interfaces [ ]. Vibrational relaxation times have also been measured for a number of modes such as the 0-Fl stretching m silica and the C-0 stretching in carbon monoxide adsorbed on transition metals [ ]. Pump-probe laser experiments such as these are difficult, but the field is still in its infancy, and much is expected in this direction m the near fiitiire. 

Implicitly, their data treatment assumes that the photoemission dissymmetry simply reverses direction with the enantiomer switch, equivalently to its... 

As was mentioned previously, photoemission has proved to be a valuable tool for measurement of the electronic structure of metal cluster particles. The information measured includes mapping the cluster DOS, ionization threshold, core-level positions, and adsorbate structure. These studies have been directed mainly toward elucidation of the convergence of these electronic properties towards their bulk analogues. Although we will explore several studies in detail, we can say that studies from different laboratories support the view that particles of 150 atoms or more are required to attain nearly bulk-like photoemission properties of transition and noble metal clusters. This result is probably one of the most firmly established findings in the area of small particles. 

The first photoelectric fhiorimeter was described by Jette and West in 1928. The instrument, which used two photoemissive cells, was employed for studying the quantitative effects of electrolytes upon the fluorescence of a series of substances, including quinine sulfate [5], In 1935, Cohen provides a review of the first photoelectric fluorimeters developed until then and describes his own apparatus using a very simple scheme. With the latter he obtained a typical analytical calibration curve, thus confirming the findings of Desha [33], The sensitivity of these photoelectric instruments was limited, and as a result utilization of the photomultiplier tube, invented by Zworykin and Rajchman in 1939 [34], was an important step forward in the development of suitable and more sensitive fluorometers. The pulse fhiorimeter, which can be used for direct measurements of fluorescence decay times and polarization, was developed around 1950, and was initiated by the commercialization of an adequate photomultiplier [35]. 

Of direct interest for photoemission of supported catalysts is that similar increases in the width of d-bands have been observed by Mason in UPS spectra of small metal particles deposited on amorphous carbon and silica substrates [48]. Theoretical calculations by Baetzold et al. [49] indicate that the bulk density of states is reached if Ag particles contain about 150 atoms, which corresponds to a hemispherical particle 2 nm in diameter. Concomitant with the appearance of narrowed d-bands in small particles is the occurrence of an increase in core level binding energies of up to 1 eV. The effect is mainly an initial and only partly a final state effect [48], although many authors have invoked final state - core hole screening effects as the only reason for the increased binding energy. 

All analytical methods that use some part of the electromagnetic spectrum have evolved into many highly specialized ways of extracting information. The interaction of X-rays with matter represents an excellent example of this diversity. In addition to straightforward X-ray absorption, diffraction, and fluorescence, there is a whole host of other techniques that are either directly X-ray-related or come about as a secondary result of X-ray interaction with matter, such as X-ray photoemission spectroscopy (XPS), surface-extended X-ray absorption fine structure (SEXAFS) spectroscopy, Auger electron spectroscopy (AES), and time-resolved X-ray diffraction techniques, to name only a few [1,2]. 

Visible light or other electromagnetic radiation incident on a solid, liquid, or gas can liberate electric charges. This is called photoelectricity. Ejection of electrons from the surface is usually called photoemission. Electrons or positive ions formed in a gas as the result of such radiation is called photoionization. Such a process, however, cannot charge a particle directly. The charging process in that case is a direct result of subsequent diffusion. 

Gao W, Kahn A (2001) Controlled p-doping of zinc phthalocyanine by coevaporation with tetrafluorotetracyanoquinodimethane a direct and inverse photoemission study. Appl Phys Lett 79 4040... 

The surface states observed by field-emission spectroscopy have a direct relation to the process in STM. As we have discussed in the Introduction, field emission is a tunneling phenomenon. The Bardeen theory of tunneling (1960) is also applicable (Penn and Plummer, 1974). Because the outgoing wave is a structureless plane wave, as a direct consequence of the Bardeen theory, the tunneling current is proportional to the density of states near the emitter surface. The observed enhancement factor on W(IOO), W(110), and Mo(IOO) over the free-electron Fermi-gas behavior implies that at those surfaces, near the Fermi level, the LDOS at the surface is dominated by surface states. In other words, most of the surface densities of states are from the surface states rather than from the bulk wavefunctions. This point is further verified by photoemission experiments and first-principles calculations of the electronic structure of these surfaces. 

In Chap. E, photoelectron spectroscopic methods, in recent times more and more employed to the study of actinide solids, are reviewed. Results on metals and on oxides, which are representative of two types of bonds, the metallic and ionic, opposite with respect to the problem itineracy vs. localization of 5f states, are discussed. In metals photoemission gives a photographic picture of the Mott transition between Pu and Am. In oxides, the use of photoelectron spectroscopy (direct and inverse photoemission) permits a measurement of the intra-atomic Coulomb interaction energy Uh. 

From the experimental viewpoint 1. the analysis of the variation of photoionization cross sections (affecting the intensities of photoelectron spectroscopy), gives an insight into the orbital composition of the bands of the solid 2. the combination of direct and inverse photoemission provides a powerful tool to assess the structure of occupied and of empty states, and, in the case of localized 5 f states, permits the determination of a fundamental quantity, the Coulomb correlation energy, governing the physical properties of narrow bands. 

By varying the excitation energy in direct and inverse photoemission, further important information is collected on hybridized states. Thus, it can be said that by photoelectron methods, the itineracy of open shells (in actinides 5f) is well characterized. 

Equation (20) may be seen as the combination of the two processes of direct and inverse photoemission, when the 5 f shell retains a strong character of localization (in case of itinerant 5fs, the Hubbard model predicts that the kinetic energy due to itineracy creates statistical fluctuations between the polar states, so that the itinerant character is lost). 

Figure 6 shows the process in a schematic way. Baer describes the two electron excitations of direct and inverse photoemission as two-step processes in which first Ep is reached and then the emission of an electron (direct) or of a photon (inverse photoemission) to vacuum occurs from Ep. A and A+ are the energies associated with the two first steps. They are counted from Ep, and they are to be considered as the minimum energies necessary to create the f and f final state. If the localized level response is a final state multiplet, therefore, Uh = A+ -I- A is given by the sum of the smallest measured energies of the multiplet. 

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