Adsorbed species electron excitation

Heterogeneous photochemical reactions fall in the general category of photochemistry—often specific adsorbate excited states are involved (see, e.g.. Ref. 318.) Photodissociation processes may lead to reactive radical or other species electronic excited states may be produced that have their own chemistry so that there is specificity of reaction. The term photocatalysis has been used but can be stigmatized as an oxymoron light cannot be a catalyst—it is not recovered unchanged. 

The second application is to the direct measurement of adsorption-desorption processes using the Auger peak height of the particular element as a monitor. The principal limitation is the possible influence of the electron beam on the adsorbate, which can result in beam-induced desorption, adsorption or dissociation. The basis of electron-stimulated desorption (ESD) was established some time ago independently be Menzel and Gomer [38] and Redhead [39]. Electron impact causes Franck—Condon transitions of bound electrons in the adsorbed species into excited states. There is, therefore, a probability of dissociation with subsequent desorption of the particular species involved. As an example of these effects on semiconductor surfaces, Joyce and Neave [40] have reported results on silicon, while Ranke and Jacobi [41] have discussed the electron-stimulated oxidation of GaAs. 

Figure C3.2.19. In this ESDIAD experiment where ions are produced and collected (see text), an adsorbed acetate species is excited by an incoming electron. ions are emitted in tire direction of tire C-H bond in tire upward pointing -CH group in tire species. Circular symmetry of figure indicates tliat C-H bonds are spinning around tire vertical axis in tire acetate species. From Lee J G, Aimer J, Mocutta D, Denev S and dates J T Jr 2000 J. Chem. Phys. 112 335.

The most common ions observed as a result of electron-stimulated desorption are atomic (e. g., H, 0, E ), but molecular ions such as OH", CO", H20, and 02" can also be found in significant quantities after adsorption of H2O, CO, CO2, etc. Substrate metallic ions have never been observed, which means that ESD is not applicable to surface compositional analysis of solid materials. The most important application of ESD in the angularly resolved form ESDIAD is in determining the structure and mode of adsorption of adsorbed species. This is because the ejection of positive ions in ESD is not isotropic. Instead the ions are desorbed along specific directions only, characterized by the orientation of the molecular bonds that are broken by electron excitation. 

Almost all Raman spectra of adsorbed species have therefore relied on enhancement effects. Thus, if the incident radiation can simultaneously excite an electronic absorption (see Figure 2.52), then the polarisabilily change associated with this change in the electronic configuration is very large. The... 

As noted in the introduction, vibrations in molecules can be excited by interaction with waves and with particles. In electron energy loss spectroscopy (EELS, sometimes HREELS for high resolution EELS) a beam of monochromatic, low energy electrons falls on the surface, where it excites lattice vibrations of the substrate, molecular vibrations of adsorbed species and even electronic transitions. An energy spectrum of the scattered electrons reveals how much energy the electrons have lost to vibrations, according to the formula ... 

Optical excitation of metals with intense femtosecond laser pulses can create extreme non-equilibrium conditions in the solid where the electronic system reaches several thousand degrees Kelvin on a sub-picosecond timescale, while the lattice (phonon) bath, stays fairly cold. As illustrated in Figure 3.22, photoexcited hot electrons may transiently attach to unoccupied adsorbate levels and this change in the electronic structure may induce vibrational motions of the adsorbate-substrate bond. For high excitation densities with femtosecond pulses, multiple excitation/deexcitation cycles can occur and may eventually lead to desorption of adsorbate molecules or reactions with co-adsorbed species. After 1-2 ps, the hot electron... 

Electron transfer takes place prior to any significant redistribution of vibrational energy in the dye s excited state. This mechanism means that injection takes place from the LCT state which is populated by the initial absorption process and that intersystem crossing to the lower-lying 3MLCT state normally observed in solution is not competitive for the adsorbed species (see Figure 6.12 above). 

In a sample containing a mixture of compounds, individual species may be resonance enhanced at different wavelengths. In some cases it may be possible to measure resonance Raman spectra from individual components in a mixture by selective excitation of specific absorption bands. Moreover, the assignment of resonance-enhanced vibrations provides detailed information about the local symmetry of the species. RRS has been used widely to characterize biological samples in which electronic transitions occur at visible excitation wavelengths, and commercial continuous wave lasers are readily available. Resonance Raman spectroscopic characterization of solid catalysts and adsorbed species has seen limited application. Many catalytic materials are white, but their electronic transitions often occur at ultraviolet wavelengths. With the availability of continuous wave and tunable, pulsed ultraviolet laser sources, we anticipate the application of RRS to catalysts will increase substantially. This expectation has motivated the present review. 

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