Polarizabilities light scattering

Equations (10.17) and (10.18) show that both the relative dielectric constant and the refractive index of a substance are measurable properties of matter that quantify the interaction between matter and electric fields of whatever origin. The polarizability is the molecular parameter which is pertinent to this interaction. We shall see in the next section that a also plays an important role in the theory of light scattering. The following example illustrates the use of Eq. (10.17) to evaluate a and considers one aspect of the applicability of this quantity to light scattering. 

Note that this also involves the assumption of isotropic molecules, which have the same polarizability in all directions. Unpolarized light consists of equal amounts of vertical and horizontal polarization, so the fraction of light scattered in the unpolarized (subscript u) case is given by... 

Cyvin, S. J., Rauch, J. E. and Decius, J. C. (1965) Theory of hyper-Raman effects (nonlinear inelastic light scattering) selection rules and depolarization ratios for the second-order polarizability. 

Raman spectroscopy is an inelastic light scattering experiment for which the intensity depends on the amplitude of the polarizability variation associated with the molecular vibration under consideration. The polarizability variation is represented by a second-rank tensor, oiXyZ, the Raman tensor. Information about orientation arises because the intensity of the scattered light depends on the orientation of the Raman tensor with respect to the polarization directions of the electric fields of the incident and scattered light. Like IR spectroscopy, Raman... 

Light Scattering. A perfectly homogeneous medium will not scatter and that scattering results from fluctuations from uniformity. The fluctuation in polarizability is defined by... 

Experimental and theoretical results are presented for four nonlinear electrooptic and dielectric effects, as they pertain to flexible polymers. They are the Kerr effect, electric field induced light scattering, dielectric saturation and electric field induced second harmonic generation. We show the relationship between the dipole moment, polarizability, hyperpolarizability, the conformation of the polymer and these electrooptic and dielectric effects. We find that these effects are very sensitive to the details of polymer structure such as the rotational isomeric states, tacticity, and in the case of a copolymer, the comonomer composition. 

We have shown in this paper the relationships between the fundamental electrical parameters, such as the dipole moment, polarizability and hyperpolarizability, and the conformations of flexible polymers which are manifested in a number of their electrooptic and dielectric properties. These include the Kerr effect, dielectric polarization and saturation, electric field induced light scattering and second harmonic generation. Our experimental and theoretical studies of the Kerr effect show that it is very useful for the characterization of polymer microstructure. Our theoretical studies of the NLDE, EFLS and EFSHG also show that these effects are potentially useful, but there are very few experimental results reported in the literature with which to test the calculations. More experimental studies are needed to further our understanding of the nonlinear electrooptic and dielectric properties of flexible polymers. 

From nonlinear light scattering in methane. Maker 26O) deduced values for the second-order polarizability. 

A short review of light scattering from biphasic systems will be helpful We shall consider the scattering to arise from a two-phase medium with average polarizability a and local inhomogeneities n(r) a(r)-a ... 

Optical activity in light scattering thus arises from interference between the molecular polarizability and optical activity tensors. 

It might seem at first glance that arriving at the dipole moment p of an ellipsoidal particle via the asymptotic form of the potential < p is a needlessly complicated procedure and that p is simply t>P, where v is the particle volume. However, this correspondence breaks down for a void, in which P, = 0, but which nonetheless has a nonzero dipole moment. Because the medium is, in general, polarizable, uP, is not equal to p even for a material particle except when it is in free space. In many applications of light scattering and absorption by small particles—in planetary atmospheres and interstellar space, for example—this condition is indeed satisfied. Laboratory experiments, however, are frequently carried out with particles suspended in some kind of medium such as water. It is for this reason that we have taken some care to ensure that the expressions for the polarizability of an ellipsoidal particle are completely general. 

In order to be able to use the fluctuation of the intensity around the average value, we need to find a way to represent the fluctuations in a convenient manner. In Section 5.3b in our discussion of Rayleigh scattering applied to solutions, we came across the concept of fluctuations of polarizabilities and concentration of scatterers and the role they play in light scattering experiments. In the present section, what we are interested in is the time dependence of such fluctuations. In general, it is not convenient to deal with detailed records of the fluctuations of a measured quantity as a function of time. Instead, one reduces the details of the fluctuations to what is known as the autocorrelation function C(s,td), as defined below ... 

Several types of collision-induced light scattering spectra are known. We have already mentioned the depolarized translational spectra of rare gas pairs and bigger complexes which arise from the anisotropy of the diatom polarizability. Contrary to the infrared inactivity of like pairs, e.g., Ar-Ar like pairs are Raman active. Furthermore, polarized translational spectra... 

As has been pointed out (63), this is a rather artificial model and, moreover, its application is quite unnecessary. In fact, (a> can be calculated from the refractive index increment (dnjdc), as has extensively been done in the field of light scattering. This procedure is applicable also to the form birefringence effect of coil molecules, as the mean excess polarizability of a coil molecule as a whole is not influenced by the form effect. It is still built up additively of the mean excess polarizabilities of the random links. This reasoning is justified by the low density of links within a coil. In fact, if the coil is replaced by an equivalent ellipsoid consisting of an isotropic material of a refractive index not very much different from that of the solvent, its mean excess polarizability is equal to that of a sphere of equal volume [cf. also Bullough (145)]. 

First of all, why are the electromagnetic properties of molecules worth investigation There are generally two reasons, the first of which is to enable one to calculate experimentally useful quantities in order to make new predictions apart from multipoles and polarizabilities themselves there are quantities that arise in the theory of the interaction between radiation and matter it is trite but true to say that the whole of spectroscopy and of light scattering depend on electromagnetic properties. In many... 

Depolarized scattering occurs because of various forms of particle anisotropy. Distinct classes of depolarizing scatterers include nonspherical particles with uniform isotropic (scalar) polarizabilities (sometimes called form anisotropy), inhomogeneous particles with nonuniform distributions of isotropic polarizability, and particles with anisotropic (tensor) polarizabilities. For each of these classes, the intensity of depolarized light scattered by a particle will change as the particle translates, rotates, or manifests internal rearrangement of its scattering elements. DDLS can provide information on the dynamics of each of these processes. 

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