Reactions molecule-surface

For example, energy transfer in molecule-surface collisions is best studied in nom-eactive systems, such as the scattering and trapping of rare-gas atoms or simple molecules at metal surfaces. We follow a similar approach below, discussing the dynamics of the different elementary processes separately. The surface must also be simplified compared to technologically relevant systems. To develop a detailed understanding, we must know exactly what the surface looks like and of what it is composed. This requires the use of surface science tools (section B 1.19-26) to prepare very well-characterized, atomically clean and ordered substrates on which reactions can be studied under ultrahigh vacuum conditions. The most accurate and specific experiments also employ molecular beam teclmiques, discussed in section B2.3. 

On the atomic level, etching is composed of several steps diflfiision of the etch molecules to the surface, adsorption to the surface, subsequent reaction with the surface and, finally, removal of the reaction products. The third step, that of reaction between the etchant and the surface, is of considerable interest to the understanding of surface reactions on an atomic scale. In recent years, STM has given considerable insight into the nature of etching reactions at surfaces. The following discussion will focus on the etching of silicon surfaces [28]. 

Because of the inherently destructive nature of ion bombardment, the use of SSIMS alone in the study of the reactions of surfaces with gases and vapor must be viewed with caution, but in combination with other surface techniques it can provide valuable additional information. The parallel techniques are most often XPS,TDS, and LEED, and the complementary information required from SSIMS normally refers to the nature of molecules on surfaces and with which other atoms, if any, they are combined. 

In a recent paper [11] this approach has been generalized to deal with reactions at surfaces, notably dissociation of molecules. A lattice gas model is employed for homonuclear molecules with both atoms and molecules present on the surface, also accounting for lateral interactions between all species. In a series of model calculations equilibrium properties, such as heats of adsorption, are discussed, and the role of dissociation disequilibrium on the time evolution of an adsorbate during temperature-programmed desorption is examined. This approach is adaptable to more complicated systems, provided the individual species remain in local equilibrium, allowing of course for dissociation and reaction disequilibria. 

Hydrogen abstraction reactions potential surfaces for, 25-26,26,41 resonance structures for, 24 Hydrogen atom, 2 Hydrogen bonds, 169,184 Hydrogen fluoride, 19-20, 20,22-23 Hydrogen molecules, 15-18 energy of, 11,16,17 Hamiltonian for, 4,15-16 induced dipoles, 75,125 lithium ion effect on, 12... 

The characteristic times on which catalytic events occur vary more or less in parallel with the different length scales discussed above. The activation and breaking of a chemical bond inside a molecule occurs in the picosecond regime, completion of an entire reaction cycle from complexation between catalyst and reactants through separation from the product may take anywhere between microseconds for the fastest enzymatic reactions to minutes for complicated reactions on surfaces. On the mesoscopic level, diffusion in and outside pores, and through shaped catalyst particles may take between seconds and minutes, and the residence times of molecules inside entire reactors may be from seconds to, effectively, infinity if the reactants end up in unwanted byproducts such as coke, which stay on the catalyst. 

In Lab 17.1, you learned about the effect of temperature and concentration on reaction rate. Another factor that affects reaction rate is the amount of surface area of the reactants. If a chemical reaction is to take place, the molecules of reactants must collide. Changing the amount of surface area modifies the rate of collision, and, thus, the rate of reaction. If surface area increases, collision frequency increases. If surface area decreases, so does the number of collisions. In this lab, you will examine the effect of surface area on rate of reaction. You will also determine how a combination of factors can affect reaction rate. 

Finally, some details of the dynamics of NO conversion reactions on surfaces have been recently probed by using angle-resolved TPD. For instance, in a study of the decomposition of N20 on Rh(110), Matsushima and co-workers have identified four N2 peaks between 60 and 150 K originating from direct N20-dissociation, and a fifth feature at 160 K attributed to the desorption of N2 molecules adsorbed on the surface after previous decomposition (Figure 3.2) [20]. The appearance of each of these peaks... 

Photoinduced electron transfer reactions between surface bound dye molecules and semiconductor electrodes are important for practical as well as fundamental reasons. Absorption of light by the dye can improve the spectral response of the semiconductor and these systems are models for the photographic process (47-511. MDC surfaces are excellent substrates for studying electron injection into the conduction band of the semiconductor. 

These descriptors have been widely used for the past 25 years to study chemical reactivity, i.e., the propensity of atoms, molecules, surfaces to interact with one or more reaction partners with formation or rupture of one or more covalent bonds. Kinetic and/or thermodynamic aspects, depending on the (not always obvious and even not univoque) choice of the descriptors were hereby considered. In these studies, the reactivity descriptors were used as such or within the context of some principles of which Sanderson s electronegativity equalization principle [16], Pearson s hard and soft acids and bases (HSAB) principle [17], and the maximum hardness principle [17,18] are the three best known and popular examples. 

The observations of complex dynamics associated with electron-stimulated desorption or desorption driven by resonant excitation to repulsive electronic states are not unexpected. Their similarity to the dynamics observed in the visible and near-infrared LID illustrate the need for a closer investigation of the physical relaxation mechanisms of low energy electron/hole pairs in metals. When the time frame for reaction has been compressed to that of the 10 s laser pulse, many thermal processes will not effectively compete with the effects of transient low energy electrons or nonthermal phonons. It is these relaxation channels which might both play an important role in the physical or chemical processes driven by laser irradiation of surfaces, and provide dramatic insight into subtle details of molecule-surface dynamics. 

One formalism which has been extensively used with classical trajectory methods to study gas-phase reactions has been the London-Eyring-Polanyi-Sato (LEPS) method . This is a semiempirical technique for generating potential energy surfaces which incorporates two-body interactions into a valence bond scheme. The combination of interactions for diatomic molecules in this formalism results in a many-body potential which displays correct asymptotic behavior, and which contains barriers for reaction. For the case of a diatomic molecule reacting with a surface, the surface is treated as one body of a three-body reaction, and so the two-body terms are composed of two atom-surface interactions and a gas-phase atom-atom potential. The LEPS formalism then introduces adjustable potential energy barriers into molecule-surface reactions. 

Studies of H2 have proven the feasibility of using the LEPS formalism to study gas-surface reactions, and have indicated that relationships between the potential surface and chemical dynamics derived from gas-phase studies can be generalized to reactions with surfaces. Reactions of H2, however, represent simple systems compared even to other diatomic molecules, and extensions to other more complicated reactions are rare. A few studies of other diatomic... 

For some steps the apparent activation energy is to be used in Eq. (10), and in others, the true activation energy. See text. (2) Where relevant, it is assumed that the symmetry number approximates unity it is also assumed that (Ijs) a 0.5, where s is the number of sites adjacent to a given site in a surface bimolecular reaction. (3) Both Cj, gas concentration in molecules cm", and P, gas pressure in atmospheres are used in this work. For an ideal gas, c, = 7.34 x 1q2i pij< 4 Except where otherwise noted, ft a 1. (5) An adsorption reaction is a Rideal-Eley reaction a surface reaction is a "Langrauir-Hinshelwood reaction. 

Farin, D. Avnir, D. (1989) The fractal nature of molecule-surface interactions and reactions. In Avnir, D. (ed.) The fractal approach to heterogenous chemistry. Wiley, New York, 271-294... 

AU reactions occur by collisions between molecules or by collisions of molecules with surfaces. We will consider reactions at surfaces later, but here we consider the theory of homogeneous reactions. We wiU not attempt a quantitative or thorough description of reaction mechanisms but will only describe them in enough detail to be able to see how the engineer can control them. These collisions occur as sketched in Figure 4-12. 

Liu, H. B. and Hamers, R. J. Stereoselectivity in molecule-surface reactions Adsorption of ethylene on the silicon(OOl) surface. Journal of the American Chemical Society 119, 7593 (1997). 

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