Chemisorption molecular

Optical second harmonic generation (SHG), which is the conversion of two photons of frequency u to a single photon of frequency 2co, is known to be an inherently surface-sensitive technique, because it requires a noncentrosymmetrical medium. At the interface between two centrosymmetrical media, such as the interface between two liquids, only the molecules which participate in the asymmetry of the interface will contribute to the SHG [18]. SHG has been used as an in-situ probe of chemisorption, molecular orientation, and... 

Thermal accommodation 1st stage of chemisorption molecular transient Dissociative chemisorption with formation of hot transient O 5 (s)... 

Catalysis, which typically requires bond rupture of the adsorbate (e.g., H2 2H), is a problem in chemisorption. Molecular dissociation is described as a two-step process... 

The solid-gas interface and the important topics of physical adsorption, chemisorption, and catalysis are addressed in Chapters XVI-XVIII. These subjects marry fundamental molecular studies with problems of great practical importance. Again the emphasis is on the basic aspects of the problems and those areas where modeling complements experiment. 

MBRS Molecular beam spectroscopy [158] A modulated molecular beam hits the surface and the time lag for reaction products is measured Kinetics of surface reactions chemisorption... 

The molecular emphasis of modem chemisorption studies has benefited the field of catalysis by giving depth and scope to the surface chemistry of catalytic processes. To paraphrase King [1], quantitative answers have become possible to the following questions ... 

The plan of this chapter is as follows. We discuss chemisorption as a distinct topic, first from the molecular and then from the phenomenological points of view. Heterogeneous catalysis is then taken up, but now first from the phenomenological (and technologically important) viewpoint and then in terms of current knowledge about surface structures at the molecular level. Section XVIII-9F takes note of the current interest in photodriven surface processes. 

Sequences such as the above allow the formulation of rate laws but do not reveal molecular details such as the nature of the transition states involved. Molecular orbital analyses can help, as in Ref. 270 it is expected, for example, that increased strength of the metal—CO bond means decreased C=0 bond strength, which should facilitate process XVIII-55. The complexity of the situation is indicated in Fig. XVIII-24, however, which shows catalytic activity to go through a maximum with increasing heat of chemisorption of CO. Temperature-programmed reaction studies show the presence of more than one kind of site [99,1(K),283], and ESDIAD data show both the location and the orientation of adsorbed CO (on Pt) to vary with coverage [284]. 

Atom abstraction occurs when a dissociation reaction occurs on a surface in which one of the dissociation products sticks to the surface, while another is emitted. If the chemisorption reaction is particularly exothennic, the excess energy generated by chemical bond fomiation can be chaimelled into the kinetic energy of the desorbed dissociation fragment. An example of atom abstraction involves the reaction of molecular halogens with Si surfaces [27, 28]. In this case, one halogen atom chemisorbs while the other atom is ejected from the surface. 

J Rettner C T and Mullins C B 1991 Dynamics of the chemisorption of O2 on Pt(111) Dissociation via direct population of a molecularly chemisorbed precursor at high incidence kinetic energy J. Chem. Phys. 94 1626... 

Figure A3.10.23 Schematic diagram of molecular CO chemisorption on a metal surface. The model is based on a donor-acceptor scheme where the CO 5 a FIOMO donates charge to surface unoccupied states and the surface back-donates charge to the CO 2 71 LUMO [58].

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. 

NakatsujI H and Nakal H 1990 Theoretical study on molecular and dissociative chemisorptions of an O2 molecule on an Ag surface dipped adcluster model combined with symmetry-adapted cluster-configuration interaction method Chem. Phys. Lett. 174 283-6... 

Pisani C 1978 Approach to the embedding problem in chemisorption in a self-consistent-field-molecular-orbital formalism Phys. Rev. B 17 3143... 

If the spent fuel is processed in a nuclear fuel reprocessing plant, the radioactive iodine species (elemental iodine and methyl iodide) trapped in the spent fuel elements ate ultimately released into dissolver off gases. The radioactive iodine may then be captured by chemisorption on molecular sieve 2eohtes containing silver (89). 

The mechanism of the synthesis reaction remains unclear. Both a molecular mechanism and an atomic mechanism have been proposed. Strong support has been gathered for the atomic mechanism through measurements of adsorbed nitrogen atom concentrations on the surface of model working catalysts where dissociative N2 chemisorption is the rate-determining step (17). The likely mechanism, where (ad) indicates surface-adsorbed species, is as follows ... 

The conclusion is that for chemisorption measurements in a CSTR, the matter in the empty space must be minimized, which calls for low (atmospheric) pressure, and low concentration of the chemical, in a low flow of carrier gas. Even at low pressure it will work only for very large surface area materials, like molecular sieves or active charcoals. 

Physisorption occurs when, as a result of energy differences and/or electrical attractive forces (weak van der Waals forces), the adsorbate molecules become physically fastened to the adsorbent molecules. This type of adsorption is multilayered that is, each molecular layer forms on top of the previous layer with the number of layers being proportional to the contaminant concentration. More molecular layers form with higher concentrations of contaminant in solution. When a chemical compound is produced by the reaction between the adsorbed molecule and the adsorbent, chemisorption occurs. Unlike physisorption, this process is one molecule thick and irreversible... 

M. Menon and R. E. AUen, New technique for molecular-dynamics computer simulations Hellmann- Feynman theorem and subspace Hamiltonian approach , Phys. Rev. B33 7099 (1986) Simulations of atomic processes at semiconductor surfaces General method and chemisorption on GaAs(llO) , ibid B38 6196 (1988). 

Figure 2. I. Spatial distribution of the main orbitals of N2 involved in molecular chemisorption on iron promoted by potassium (K or K20). Arrows indicate the direction of transfer of electron density.5...

Table 2.1. Dissociative (D) and molecular (M) chemisorption of CO on metal surfaces.

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