Electromagnetic radiation dispersion

In this section we consider electromagnetic dispersion forces between macroscopic objects. There are two approaches to this problem in the first, microscopic model, one assumes pairwise additivity of the dispersion attraction between molecules from Eq. VI-15. This is best for surfaces that are near one another. The macroscopic approach considers the objects as continuous media having a dielectric response to electromagnetic radiation that can be measured through spectroscopic evaluation of the material. In this analysis, the retardation of the electromagnetic response from surfaces that are not in close proximity can be addressed. A more detailed derivation of these expressions is given in references such as the treatise by Russel et al. [3] here we limit ourselves to a brief physical description of the phenomenon. 

The focus of this chapter is photon spectroscopy, using ultraviolet, visible, and infrared radiation. Because these techniques use a common set of optical devices for dispersing and focusing the radiation, they often are identified as optical spectroscopies. For convenience we will usually use the simpler term spectroscopy in place of photon spectroscopy or optical spectroscopy however, it should be understood that we are considering only a limited part of a much broader area of analytical methods. Before we examine specific spectroscopic methods, however, we first review the properties of electromagnetic radiation. 

In the second broad class of spectroscopy, the electromagnetic radiation undergoes a change in amplitude, phase angle, polarization, or direction of propagation as a result of its refraction, reflection, scattering, diffraction, or dispersion by the sample. Several representative spectroscopic techniques are listed in Table 10.2. 

All spectrometers have the following basic units a source of electromagnetic radiation, a dispersion device, sample holder, optical devices for collimating and focusing, a detection device and a data readout or storage system. There are also a variety of ways in which these parts are assembled into the entire spectrometer. 

As with prisms, there are other devices that have been historically used for dispersing or filtering electromagnetic radiation. These include interference filters and absorption filters. Both of these are used for monochromatic instruments or experiments and find little use compared to more versatile instruments. The interested reader is referred to earlier versions of instrumental analysis texts. 

An X-ray fluorescence spectrometer needs to resolve the different peaks, identify them and measure their area to quantify the data. There are two forms of X-ray spectrometers (Fig. 5.5), which differ in the way in which they characterize the secondary radiation - wavelength dispersive (WD), which measures the wavelength, and energy dispersive (ED), which measures the energy of the fluorescent X-ray (an illustration of the particle-wave duality nature of electromagnetic radiation, described in Section 12.2). 

The basic layout of a simple dispersive IR spectrometer is the same as for an UV spectrometer (Figure 2.1), except that all components must now match the different energy range of electromagnetic radiation. The more sophisticated Fourier Transform Infrared (FTIR) instruments record an infrared interference pattern generated by a moving mirror and this is transformed by a computer into an infrared spectrum. 

A dispersive phenomenon occurring when the wavelength of scattered electromagnetic radiation in the mid-infrared spectral region is shifted relative to that of the incident beam of exciting radiation. Spectral excitation is typically measured at a nonabsorbing wavelength, and the Raman effect occurs when the polarizabihty of a bond varies with the internuclear distance, as specified by the equation ... 

Like other phenomena involving interactions between electromagnetic radiation and organic molecules, as in infrared, ultraviolet, and nmr spectroscopy, optical rotatory dispersion curves often are quite sensitive to small changes in structure. As an example, the rotatory dispersion curves for enantiomers of cis- and trcMr-lO-methyl-2-decalones, 16 and 17, are reproduced in Figure 19-7 ... 

A spectroscope is an instrument used to disperse a beam of electromagnetic radiation into its component waves. Many spectroscopes have diffraction gratings that separate the waves, which are beamed to a mirror and reflected back to the eye of an observer. Each wave appears as a separate colored line. 

In ionic and partially ionic crystals optic vibrations are associated with strong electric moments and hence can interact directly with the transverse electric field of incident infrared electromagnetic radiation. In terms of the phenomenological theory of infrared dispersion, if , and D are the electric field, polarization and displacement vectors respectively, then... 

In the past, the study of matter and Its Interaction with radiation was largely confined to the measurement of electromagnetic radiation. The excitation and de-excltatlon of atoms and molecules by photons emitted or absorbed when electrons made transitions between different discrete states has been well studied. Scanning electron microscopy (SEM), for example, makes routine use of energy dispersive X-ray analysis (EDX). In this case the sample emits X rays as a by-product of the technique. 

In classical optical absorption measurements, the absorption of a sample under different conditions as a function of the energy of the incident electromagnetic radiation is studied. This can be achieved in two ways one can either take a broadband source and use a spectrometer to disperse the electromagnetic spectrum, or use a monochromatic tunable source. There is also a... 

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