Atomic orientation experiments

Solid metal surfaces contain numerous defects such as atomic steps, point defects and dislocations and grain boundaries that ean influence double layer properties. Most basic experiments on the structure of the eleetric double layer are therefore carried out on liquid electrodes, mostly mercury. This also avoids problems related to rugosity and crystal orientation. Experiments with polycrystalline solids yield an average value for the double layer properties of the electrode-solution interface. 

Since the pioneering demonstration that cross-polarization C NMR spectra can be recorded, solid-state NMR spectroscopy has advanced rapidly and is now being used to study the structure and dynamics of a variety of polymer systems. Much of the success of solid-state NMR spectroscopy is due to the evolution of a variety of techniques for studying internuclear distances, anisotropy, torsion angles, atomic orientations, spin diffusion, molecular dynamics, and exchange processes, while maintaining the high resolution and sensitivity necessary for practically useful NMR experiments in polymers. 

The nature of reaction products and also the orientation of adsorbed species can be studied by atomic beam methods such as electron-stimulated desorption (ESD) [49,30], photon-stimulated desoiption (PDS) [51], and ESD ion angular distribution ESDIAD [51-54]. (Note Fig. VIII-13). There are molecular beam scattering experiments such... 

The structure of a fluid is characterized by the spatial and orientational correlations between atoms and molecules detemiiued through x-ray and neutron diffraction experiments. Examples are the atomic pair correlation fiinctions (g, g. . ) in liquid water. An important feature of these correlation functions is that... 

Polar molecules, like nonpolar molecules, are attracted to one another by dispersion forces. In addition, they experience dipole forces as illustrated in Figure 9.9, which shows the orientation of polar molecules, such as Id, in a crystal. Adjacent molecules line up so that the negative pole of one molecule (small Q atom) is as dose as possible to the positive pole (large I atom) of its neighbor. Under these conditions, there is an electrical attractive force, referred to as a dipole force, between adjacent polar molecules. 

Such simple considerations led Scholten and Konvalinka to confirm the form of the dependence of the reaction velocity on the pressure, as had been observed in their experiments. Taking into account a more realistic situation, on the polycrystalline hydride surface with which a hydrogen molecule is dealing when colliding and subsequently being dissociatively adsorbed, we should assume rather a different probability of an encounter with a hydride center of a /3-phase lattice, an empty octahedral hole, or a free palladium atom—for every kind of crystallite orientation on the surface, even when it is represented, for the sake of simplicity, by only the three low index planes. 

At one extreme, one has the structural models of perfect crystals, which have long-range positional order for all the atoms (apart thermal motion). A diffraction experiment on a set of such crystals oriented in one direction (corresponding, in most real cases of polymeric materials, to an oriented fiber) would result in a pattern of sharp reflections organized in layer lines. 

If a spinning electron behaved like a spinning ball, the axis of spin could point in any direction. The electron would behave like a bar magnet that could have any orientation relative to the applied magnetic field. In that case, a broad band of silver atoms should appear at the detector, because the field would push the silver atoms by different amounts according to the orientation of the spin. Indeed, that is exactly what Stem and Gerlach observed when they first carried out the experiment. 

Now that we have a model, we must check its consistency with various experiments. Sometimes such inconsistencies result in the complete rejection of a model. More often, they indicate that we need to refine the model. In the present case, the results of careful experiments show that the collision model of reactions is not complete, because the experimental rate constant is normally smaller than predicted by collision theory. We can improve the model by realizing that the relative direction in which the molecules are moving when they collide also might matter. That is, they need to be oriented a certain way relative to each other. For example, the results of experiments of the kind described in Box 13.2 have shown that, in the gas-phase reaction of chlorine atoms with HI molecules, HI + Cl — HC1 I, the Cl atom reacts with the HI molecule only if it approaches from a favorable direction (Fig. 13.28). A dependence on direction is called the steric requirement of the reaction. It is normally taken into account by introducing an empirical factor, P, called the steric factor, and changing Eq. 17 to... 

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