Ultraviolet photoelectron

Ultraviolet photoelectron spectroscopy (UPS) is a variety of photoelectron spectroscopy that is aimed at measuring the valence band, as described in sectionBl.25.2.3. Valence band spectroscopy is best perfonned with photon energies in the range of 20-50 eV. A He discharge lamp, which can produce 21.2 or 40.8 eV photons, is commonly used as the excitation source m the laboratory, or UPS can be perfonned with synchrotron radiation. Note that UPS is sometimes just referred to as photoelectron spectroscopy (PES), or simply valence band photoemission. 

Ultraviolet photoelectron spectroscopy (UPS) results have provided detailed infomiation about CO adsorption on many surfaces. Figure A3.10.24 shows UPS results for CO adsorption on Pd(l 10) [58] that are representative of molecular CO adsorption on platinum surfaces. The difference result in (c) between the clean surface and the CO-covered surface shows a strong negative feature just below the Femii level ( p), and two positive features at 8 and 11 eV below E. The negative feature is due to suppression of emission from the metal d states as a result of an anti-resonance phenomenon. The positive features can be attributed to the 4a molecular orbital of CO and the overlap of tire 5a and 1 k molecular orbitals. The observation of features due to CO molecular orbitals clearly indicates that CO molecularly adsorbs. The overlap of the 5a and 1 ti levels is caused by a stabilization of the 5 a molecular orbital as a consequence of fomiing the surface-CO chemisorption bond. 

Figure Bl.19.4. (a) Local conductance STS measurements at specific points within the Si(l 11)-(7 x 7) unit cell (symbols) and averaged over whole cell, (b) Equivalent data obtained by ultraviolet photoelectron spectroscopy (UPS) and inverse photoemission spectroscopy (IPS). (Taken from [19], figure 2.)...

Briggs D (ed) 1978 Handbook of X-ray and Ultraviolet Photoelectron Spectroscopy (London Fleyden)... 

Ultraviolet photoelectron spectroscopy (UPS) [2, 3 and 4, 6] differs from XPS in that UV light (He I, 21.2 eV He II, 40.8 eV) is used instead of x-rays. At these low excitmg energies, photoemission is limited to valence electrons. 

Figure Bl.26.22. The energy width W of an ultraviolet photoelectron spectrum from a solid may be used to detemiine the work fimction. Changes in work fimction may be obtained from changes in the cut-off of the secondary electron peak (inset) (Attard G and Bames C 1988 Surfaces (Oxford Oxford University Press)).

Cheshnovsky O, Yang S H, Pettiette C L, Craycraft M J, Liu Y and Smalley R E 1987 Ultraviolet photoelectron spectroscopy of semiconductor clusters silicon and germanium Chem. Phys. Lett. 138 119... 

Ultraviolet photoelectron spectroscopy allows the determination of ionization potentials. For thiazole the first experimental measurement using this technique was preformed by Salmona et al. (189) who later studied various alkyl and functional derivatives in the 2-position (190,191). Substitution of an hydrogen atom by an alkyl group destabilizes the first ionization potential, the perturbation being constant for tso-propyl and heavier substituents. Introduction in the 2-position of an amino group strongly destabilizes the first band and only slightly the second. 

Figure 8.1 Processes occurring in (a) ultraviolet photoelectron spectroscopy (UPS), (b) X-ray photoelectron spectroscopy (XPS) and (c) Auger electron spectroscopy (AES)...

A monochromator is useful not only for removing unwanted lines from the X-ray source but also for narrowing the otherwise broad lines. For example, each of the MgXa and AlXa doublets is unresolved and about 1 cY wide at half-intensity. A monochromator can reduce this to about 0.2 cY This reduction of the line width is very important because in an XPS specttum, unlike an ultraviolet photoelectron specttum, the resolution is limited by the line width of the ionizing radiation. Unfortunately, even after line narrowing to 0.2 cY... 

The He I ultraviolet photoelectron spectra of Kr and Xe appear similar to that of Ar but the ionization energy decreases and the spin-orbit coupling increases with increasing atomic number, as illustrated by the data in Table 8.1. 

Figure 8.6 The He I ultraviolet photoelectron spectrum of argon. (Reproduced from Turner, D. W., Baker, C., Baker, A. D. and Brundle, C. R., Molecular Photoelectron Spectroscopy, p. 41, John Wiley, London, 1970)...

Question. Which low-lying states of NO would you expect to feature in the He I ultraviolet photoelectron spectrum of NO (Consider removal of an electron from only the three outermost orbitals of NO.) Indicate whether a long or short vibrational progression would be anticipated in each case. 

Figure 8.12 The He I ultraviolet photoelectron spectrum of benzene. (Reproduced from Karlsson, L., Mattsson, L., Jadmy, R., Bergmark, T. and Siegbahn, K., Physica Scripta, 14, 230, 1976)...

Both UPS and XPS of solids are useful techniques. So far as studies of adsorption by surfaces are concerned we would expect UPS, involving only valence orbitals, to be more sensitive. For example, if we wish to determine whether nitrogen molecules are adsorbed onto an iron surface with the axis of the molecule perpendicular or parallel to the surface it would seem that the valence orbitals would be most affected. This is generally the case but, because ultraviolet photoelectron spectra of solids are considerably broadened, it is the X-ray photoelectron spectra that are usually the most informative. 

What would you expect to be the most important features of the He 1 ultraviolet photoelectron spectmm of mercury vapour ... 

Make measurements of band positions in the ultraviolet photoelectron spectmm in Figure 8.7 as accurately as you can and use these to determine cOg and cOgXg (Equations 7.82 and 6.18) for the ground electronic state of Hj. 

Rabalais, J. W. (1977) Principles of Ultraviolet Photoelectron Spectroscopy, John Wiley, New York. Roberts, M. W. and McKee, C. S. (1979) Chemistry of the Metal-Gas Interface, Oxford University Press, Oxford. 

The factor limiting the resolution in ultraviolet photoelectron spectra is the inability to measure the kinetic energy of the photoelectrons with sufficient accuracy. The source of the problem points to a possible solution. If the photoelectrons could be produced with zero kinetic energy this cause of the loss of resolution would be largely removed. This is the basis of zero kinetic energy photoelectron (ZEKE-PE) spectroscopy. 

Figure 9.50 Processes involved in obtaining (a) an ultraviolet photoelectron spectrum, (b) a zero kinetic energy photoelectron (ZEKE-PE) spectrum by a one-photon process and (c) a ZEKE-PE spectrum by a two-photon process in which the first photon is resonant with an excited electronic state of the molecule...

The resolution of the ZEKE-PE spectmm of 1,4-difluorobenzene can be compared with, for example, that of the ultraviolet photoelectron spectmm of benzene in Figure 8.12. The greatly increased resolution in the ZEKE-PE spectmm is attributable mostly to the fact that only photoelectrons with zero kinetic energy are being detected. It is also partly attributable to the molecules being in a supersonic jet this has the effect of sharpening the bands because of the restricted rotational populations in the ground state of the molecule. 

Other techniques in which incident photons excite the surface to produce detected electrons are also Hsted in Table 1. X-ray photoelectron Spectroscopy (xps), which is also known as electron spectroscopy for chemical analysis (esca), is based on the use of x-rays which stimulate atomic core level electron ejection for elemental composition information. Ultraviolet photoelectron spectroscopy (ups) is similar but uses ultraviolet photons instead of x-rays to probe atomic valence level electrons. Photons are used to stimulate desorption of ions in photon stimulated ion angular distribution (psd). Inverse photoemission (ip) occurs when electrons incident on a surface result in photon emission which is then detected. 

C. L. Wilson, Comprehensive Analytical Chemisty Ultraviolet Photoelectron and Photoion Spectroscopy Auger Electron Spectroscopy Plasma Excitation in SpectrochemicalAnalysis, Vol. 9, Elsevier Science, Inc., New York, 1979. 

NIRMS = noble-gas-ion reflection mass spectrometry OSEE = optically stimulated exoelectron emission PES = photoelectron spectroscopy PhD = photoelectron diffraction SIMS = secondary ion mass spectroscopy UPS = ultraviolet photoelectron spectroscopy ... 

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