Surface probes

Optical second-harmonic generation (SHG) has recently emerged as a powerful surface probe [95, 96]. Second harmonic generation has long been used to produce frequency doublers from noncentrosymmetric crystals. As a surface probe, SHG can be caused by the break in symmetry at the interface between two centrosymmetric media. A high-powered pulsed laser is focused at an angle of incidence from 30 to 70° onto the sample at a power density of 10 to 10 W/cm. The harmonic is observed in reflection or transmission at twice the incident frequency with a photomultiplier tube. 

Electrons are extremely usefiil as surface probes because the distances that they travel within a solid before scattering are rather short. This implies that any electrons that are created deep within a sample do not escape into vacuum. Any technique that relies on measurements of low-energy electrons emitted from a solid therefore provides infonuation from just the outenuost few atomic layers. Because of this inlierent surface sensitivity, the various electron spectroscopies are probably the most usefid and popular teclmiques in surface science. 

Shen Y R 1994 Surfaces probed by nonlinear optics Surf. Sc/. 299-300 551... 

In order to verify the presence of bimetallic particles having mixed metal surface sites (i.e., true bimetallic clusters), the methanation reaction was used as a surface probe. Because Ru is an excellent methanation catalyst in comparison to Pt, Ir or Rh, the incorporation of mixed metal surface sites into the structure of a supported Ru catalyst should have the effect of drastically reducing the methanation activity. This observation has been attributed to an ensemble effect and has been previously reported for a series of silica-supported Pt-Ru bimetallic clusters ( ). 

Methanatlon Studies. Because the most effective way to determine the existence of true bimetallic clusters having mixed metal surface sites Is to use a demanding catalytic reaction as a surface probe, the rate of the CO methanatlon reaction was studied over each series of supported bimetallic clusters. Turnover frequencies for methane formation are shown In Fig. 2. Pt, Ir and Rh are all poor CO methanatlon catalysts In comparison with Ru which Is, of course, an excellent methanatlon catalyst. Pt and Ir are completely inactive for methanatlon In the 493-498K temperature range, while Rh shows only moderate activity. 

Rodriguez P, Herrero E, Aldaz A, Fehu JM. 2006. Tellurium adatoms as an in-sim surface probe of (111) two-dimensional domains at platinum surfaces. Langmuir 22 10329-10337. 

Shen YR. 1994. Surfaces probed by nonlinear optics. Surf Sci 300 551-562. 

Benmouna, F. and Johannsmann, D. (2004). Viscoelasticity of gelatin surfaces probed by AFM noise analysis. Langmuir 20,188-193. 

In the following sections, studies of isomeric ions are reported in which the ions are reactively probed. Where calculations are available, information on potential energy surfaces is given. This is usually the structure of the stable isomeric forms and transition states and their relative energies thus only points on the potential surface are known. The detailed form of the potential surface is almost never available nor is the connectivity between the various states usually established theoretically (chemical intuition is often used to connect the states). Pertinent experimental data on CID and metastable ions, isomers produced in binary reactions, and potential surfaces probed by binary reactions (with the excited isomeric ion as the reaction intermediate) are also given. 

Myelin in situ has a water content of about 40%. The dry mass of both CNS and PNS myelin is characterized by a high proportion of lipid (70-85%) and, consequently, a low proportion of protein (15-30%). By comparison, most biological membranes have a higher ratio of proteins to lipids. The currently accepted view of membrane structure is that of a lipid bilayer with integral membrane proteins embedded in the bilayer and other extrinsic proteins attached to one surface or the other by weaker linkages. Proteins and lipids are asymmetrically distributed in this bilayer, with only partial asymmetry of the lipids. The proposed molecular architecture of the layered membranes of compact myelin fits such a concept (Fig. 4-11). Models of compact myelin are based on data from electron microscopy, immunostaining, X-ray diffraction, surface probes studies, structural abnormalities in mutant mice, correlations between structure and composition in various species, and predictions of protein structure from sequencing information [4]. 

The MBPs are extrinsic proteins localized exclusively at the cytoplasmic surface in the major dense line (Fig. 4-11), a conclusion based on their amino acid sequence, inaccessibility to surface probes and direct localization at the electron microscope level by immunocytochemistry. There is evidence to suggest that MBP forms dimers, and it is believed to be the principal protein stabilizing the major dense line of CNS myelin, possibly by interacting with negatively charged lipids. A severe hypomyelination and failure of compaction of the major dense line in MBP deficient shiverer mutants supports this hypothesis (Table 4-2). 

Scheme 1 summarizes four different approaches used to characterize dendrimer structures by photophysical and photochemical probes 1. Non-covalent, inter-molecularly bound interior probes - to study the internal cavities and the encapsulation abilities of dendrimers. 2. Non-covalent, intermolecularly bound surface probes - to study surface characteristics of dendrimers. 3. Covalently linked probes on dendrimer surfaces - to study the molecular dynamics of dendrimers. 4. Covalently linked probes at the dendrimer central core - to study the site isolation of the core moiety and define the hydrodynamic volume of dendrimers by the concentric dendrimer shells. Critical literature in these four categories will be described using representative examples. 

ESR studies of other paramagnetic metal ions (Mn " ", VC)2+) as surface probes have confirmed that cation rotational mobility on fully wetted smectites with interlayer spacings of 1.0 nm or more is not more than 50% reduced relative to aqueous solution (12, 14). Apparently, about four molecular layers of water in the interlayer provide sufficient space for solution-like rotation rates of hydrated metal ions. 

After discussing specific, basic and experimental aspects of the use of thermal He as a surface probe we will review recent results obtained in the study of surface dynamics and of 2D phase transitions. 

It is primarily the exclusive surface sensitivity of thermal atom scattering which makes this method to an outstanding surface probe. This was recognized more than sixty years ago by T. H. Johnson ... 

The nautre of the He-surface interaction potential determines the major characteristics of the He beam as surface analytical tool. At larger distances the He atom is weakly attracted due to dispersion forces. At a closer approach, the electronic densities of the He atom and of the surface atoms overlap, giving rise to a steep repulsion. The classical turning point for thermal He is a few angstroms in front of the outermost surface layer. This makes the He atom sensitive exclusively to the outermost layer. The low energy of the He atoms and their inert nature ensures that He scattering is a completely nondestructive surface probe. This is particularly important when delicate phases, like physisorbed layers, are investigated. 

However, silane-based SAMs were found to be thermally stable up to a temperature of 467°C (C-C decomposition [102]). Detectable changes with surface probe microscopy and in terms of wetting behavior were reported to appear at around 125 °C [103]. 

The combined ISS/SIMS is an extremely useful surface analytical technique that can provide several types of data from the same surface. Both ISS and SIMS employ ion beams, and thereby both methods can utilize the same ion source for the surface probe, as schematically shown in Fig. 2.16. Addition of a specially designed ion lens and quadruple mass spectrometer can make the whole system much more efficient. The value of information obtained from the combination of these two systems is... 

As discussed earlier, surface trapped electrons are not only important as paramagnetic surface probes but, being localized at a solid-gas interface, they are extremely reactive and can act as powerful reducing agents leading to surface stabilized radicals. An account of these radicals has been given in the past volume of this series1 and we limit ourselves here to report on the 1702 radical stabilized on the surface of MgO for which the hyperfine tensor was fully... 

Because the technique is essentially a mass spectrometer, the detection sensitivity can be quite high, approaching 1 ppb for many elements. This advantage, the capability of analyzing all elements and readily distinguishing between isotopes, and the built-in depth-profiling ability make SIMS a very powerful qualitative surface probe. 

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