Debye factor

However, low-temperature spectroscopy, in particular the fluorescence-narrowed emission, can in principle tell one further thing about the influence of proteins on chromophores. There can be a quasi-continuous tail at energies below the ZPL peak, and it represents coupling of the dipole transition to the low-frequency modes (the phonons) of the protein or the solvent. The relative strength of the ZPL to the phonon tail is the Debye-Waller factor and is a measure of the strength of the phonon-chro-mophore coupling. The phonon band is expected to be homogeneously broadened. Unfortunately, at this point no one has been able to use low-temperature spectroscopy to resolve the ZPL and the Debye spectrum in a protein, or observe the Debye factor as a function of temperature. We look forward to these important measurements. 

The first solution for the electrophoretic mobility of a charged particle was reported by Von Smoluchowski for the case of a thin double layer (i.e., ka 1) where k is the Debye factor and a is the particle radius. Accordingly, the electrophoretic mobility of a charged particle should follow... 

The presence of isotropic thermal disorder may be accounted for multiplying the Bragg contribution to the total intensity Eq. 2 by the Debye factor ... 

Figure 15.11 Temperature-dependence of the Debye factor /d (eqn (15.7)) for the charged reactants in water along the liquid-vapour coexistence curve. An encounter distance of 0.5 nm has been assumed.

The segmental friction factor introduced in the derivation of the Debye viscosity equation is an important quantity. It will continue to play a role in the discussion of entanglement effects in the theory of viscoelasticity in the next chapter, and again in Chap. 9 in connection with solution viscosity. Now that we have an idea of the magnitude of this parameter, let us examine the range of values it takes on. 

Equation (2.61) predicts a 3.5-power dependence of viscosity on molecular weight, amazingly close to the observed 3.4-power dependence. In this respect the model is a success. Unfortunately, there are other mechanical properties of highly entangled molecules in which the agreement between the Bueche theory and experiment are less satisfactory. Since we have not established the basis for these other criteria, we shall not go into specific details. It is informative to recognize that Eq. (2.61) contains many of the same factors as Eq. (2.56), the Debye expression for viscosity, which we symbolize t . If we factor the Bueche expression so as to separate the Debye terms, we obtain... 

Inspection of Fig. 3.9 suggests that for polyisobutylene at 25°C, Ti is about lO hr. Use Eq. (3.101) to estimate the viscosity of this polymer, remembering that M = 1.56 X 10. As a check on the value obtained, use the Debye viscosity equation, as modified here, to evaluate M., the threshold for entanglements, if it is known that f = 4.47 X 10 kg sec at this temperature. Both the Debye theory and the Rouse theory assume the absence of entanglements. As a semi-empirical correction, multiply f by (M/M. ) to account for entanglements. Since the Debye equation predicts a first-power dependence of r) on M, inclusion of this factor brings the total dependence of 77 on M to the 3.4 power as observed. 

An alternative point of view assumes that each repeat unit of the polymer chain offers hydrodynamic resistance to the flow such that f-the friction factor per repeat unit-is applicable to each of the n units. This situation is called the free-draining coil. The free-draining coil is the model upon which the Debye viscosity equation is based in Chap. 2. Accordingly, we use Eq. (2.53) to give the contribution of a single polymer chain to the rate of energy dissipation ... 

Other factors that can stabili2e such a forming complex are hydrophobic bonding by a variety of mechanisms (Van der Waals, Debye, ion-dipole, charge-transfer, etc). Such forces complement the stronger hydrogen-bonding and electrostatic interactions. 

In the procedure of X-ray refinement, the positions of the atoms and their fluctuations appear as parameters in the structure factor. These parameters are varied to match the experimentally determined strucmre factor. The term pertaining to the fluctuations is the Debye-Waller factor in which the atomic fluctuations are represented by the atomic distribution tensor ... 

Note in passing that the common model in the theory of diffusion of impurities in 3D Debye crystals is the so-called deformational potential approximation with C a>)ccco,p co)ccco and J o ) oc co, which, for a strictly symmetric potential, displays weakly damped oscillations and does not have a well defined rate constant. If the system permits definition of the rate constant at T = 0, the latter is proportional to the square of the tunneling matrix element times the Franck-Condon factor, whereas accurate determination of the prefactor requires specifying the particular spectrum of the bath. 

Here Pyj is the structure factor for the (hkl) diffiaction peak and is related to the atomic arrangements in the material. Specifically, Fjjj is the Fourier transform of the positions of the atoms in one unit cell. Each atom is weighted by its form factor, which is equal to its atomic number Z for small 26, but which decreases as 2d increases. Thus, XRD is more sensitive to high-Z materials, and for low-Z materials, neutron or electron diffraction may be more suitable. The faaor e (called the Debye-Waller factor) accounts for the reduction in intensity due to the disorder in the crystal, and the diffracting volume V depends on p and on the film thickness. For epitaxial thin films and films with preferred orientations, the integrated intensity depends on the orientation of the specimen. 

Thermal properties of overlayer atoms. Measurement of the intensity of any diffracted beam with temperature and its angular profile can be interpreted in terms of a surface-atom Debye-Waller factor and phonon scattering. Mean-square vibrational amplitudes of surfece atoms can be extracted. The measurement must be made away from the parameter space at which phase transitions occur. 

Where, /(k) is the sum over N back-scattering atoms i, where fi is the scattering amplitude term characteristic of the atom, cT is the Debye-Waller factor associated with the vibration of the atoms, r is the distance from the absorbing atom, X is the mean free path of the photoelectron, and is the phase shift of the spherical wave as it scatters from the back-scattering atoms. By talcing the Fourier transform of the amplitude of the fine structure (that is, X( )> real-space radial distribution function of the back-scattering atoms around the absorbing atom is produced. 

V is the volume, and F is a factor of proportionality, which is calculable from the elastic properties of the solid. The connection with elasticity was in fact suspected by Sutherland in 1910 (Phil, May., 20, 657), who found that the infra-red frequency of a solid was of the same order as the frequency of an elastic transversal vibration with a wave length equal to the distance between two neighbouring atoms. To every degree of freedom Debye assigns an amount of energy ... 

Debye heat capacity equation 572-80 Einstein heat capacity equation 569-72 heat capacity from low-lying electronic levels 580-5 Schottky effect 580-5 statistical weight factors in energy levels of ideal gas molecule 513 Stirling s approximation 514, 615-16 Streett, W. B. 412... 

A new approach to the double-layer capacitance of rough electrodes has been given by Daikhin et al.m m The concept of a Debye length-dependent roughness factor [i.e., a roughness function R LD) that deter-... 

The Debye length of the electrode material can be determined from the constant B, and the sensitivity factor S from C, provided the diffusion length and the diffusion constant for minority carriers are known. 

Thermal diffusivity Temperature sensitivity Temperature difference Thickness of tube Aspect ratio, relation of Cp/Cy Fluid dielectric constant Wall zeta potential Dimensionless temperature Friction factor, Debye length Mean free path Dynamic viscosity Kinematic viscosity Bejan number Density... 

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