Dipole absorbing

An explanation is needed as to why the adsorption of water vapor on bare aluminum and soft steel, on the one hand, and on bare gold and platinum, on the other hand, has opposite effects on the contact potential differences. It is concluded that the water molecules adsorbed as dipoles on the first two metals are adsorbed with the negative pole outermost on the latter two metals the water dipoles absorb with the positive pole outermost. This behavior is in agreement with the conclusions reported by others. 

The optical anisotropy, as characterized by the difference between the absorption of IR light polarized in the directions parallel and perpendicular to the reference axis (i.e., the direction of applied strain), is known as the IR linear dichroism of the system. For a uniaxially oriented polymer system [10, 28-30], the dichroic difference, A/4(v) = y4 (v) - Ax v), is proportional to the average orientation, i.e., the second moment of the orientation distribution function, of transition dipoles (or electric-dipole transition moments) associated with the molecular vibration occurring at frequency v. If the average orientation of the transition dipoles absorbing light at frequency is in the direction parallel to the applied strain, the dichroic difference AA takes a positive value on the other hand, the IR dichroism becomes negative if the transition dipoles are perpendicularly oriented. 

Figure Bl.6.10 Energy-loss spectrum of 3.5 eV electrons specularly reflected from benzene absorbed on the rheniiun(l 11) surface [H]. Excitation of C-H vibrational modes appears at 100, 140 and 372 meV. Only modes with a changing electric dipole perpendicular to the surface are allowed for excitation in specular reflection. The great intensity of the out-of-plane C-H bending mode at 100 meV confimis that the plane of the molecule is parallel to the metal surface. Transitions at 43, 68 and 176 meV are associated with Rli-C and C-C vibrations.

The first term in this expansion, when substituted into the integral over the vibrational eoordinates, gives ifj(Re) , whieh has the form of the eleetronie transition dipole multiplied by the "overlap integral" between the initial and final vibrational wavefunetions. The if i(Rg) faetor was diseussed above it is the eleetronie El transition integral evaluated at the equilibrium geometry of the absorbing state. Symmetry ean often be used to determine whether this integral vanishes, as a result of whieh the El transition will be "forbidden". 

Another related issue is the computation of the intensities of the peaks in the spectrum. Peak intensities depend on the probability that a particular wavelength photon will be absorbed or Raman-scattered. These probabilities can be computed from the wave function by computing the transition dipole moments. This gives relative peak intensities since the calculation does not include the density of the substance. Some types of transitions turn out to have a zero probability due to the molecules symmetry or the spin of the electrons. This is where spectroscopic selection rules come from. Ah initio methods are the preferred way of computing intensities. Although intensities can be computed using semiempirical methods, they tend to give rather poor accuracy results for many chemical systems. 

When monochromatic radiation falls on a molecular sample in the gas phase, and is not absorbed by it, the oscillating electric field E (see Equation 2.1) of the radiation induces in the molecule an electric dipole which is related to E by the polarizability... 

Molecules initially in the J = 0 state encounter intense, monochromatic radiation of wavenumber v. Provided the energy hcv does not correspond to the difference in energy between J = 0 and any other state (electronic, vibrational or rotational) of the molecule it is not absorbed but produces an induced dipole in the molecule, as expressed by Equation (5.43). The molecule is said to be in a virtual state which, in the case shown in Figure 5.16, is Vq. When scattering occurs the molecule may return, according to the selection mles, to J = 0 (Rayleigh) or J = 2 (Stokes). Similarly a molecule initially in the J = 2 state goes to... 

The dielectric properties of most foods, at least near 2450 MH2, parallel those of water, the principal lossy constituent of food (Fig. 1). The dielectric properties of free water are well known (30), and presumably serve as the basis for absorption in most foods as the dipole of the water molecule interacts with the microwave electric field. By comparison, ice and water of crystaUi2ation absorb very Httie microwave energy. Adsorbed water, however, can retain its Hquid character below 0°C and absorb microwaves (126). 

Fig. 1. An incident electromagnetic field of intensity, having an associated electric field, U, induces dipole oscillation in the absorbers. The transmitted...

This model was later expanded upon by Lifshitz [33], who cast the problem of dispersive forces in terms of the generation of an electromagnetic wave by an instantaneous dipole in one material being absorbed by a neighboring material. In effect, Lifshitz gave the theory of van der Waals interactions an atomic basis. A detailed description of the Lifshitz model is given by Krupp [34]. 

Carbon dioxide absorbs infrared energy during bending or stretching motions that are accompanied by a change in dipole moment (from zero). Which of the transitions pictured in Fig. 2b... 

The intercept, 1/Po, is called the anisotropy of the molecule and is an indication of the nonrotational depolarization of the molecule. This intrinsic depolarization is due to the segmental motion of the fluorophores within the molecule the depolarization due to energy transfer and the angular difference in transition dipole moments of the absorbing and emitting states. 

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