Relaxation frequency dependence

The dramatic slowing down of molecular motions is seen explicitly in a vast area of different probes of liquid local structures. Slow motion is evident in viscosity, dielectric relaxation, frequency-dependent ionic conductance, and in the speed of crystallization itself. In all cases, the temperature dependence of the generic relaxation time obeys to a reasonable, but not perfect, approximation the empirical Vogel-Fulcher law ... 

The first problem is to exclude geometrical relaxation. When an electric field is applied, charges are localized on the sample under the influence of both the field and the diffusion gradient. On reversal of the field, charges find a new equilibrium so that the macroscopic dipole, the dimensions of which are those of the sample, and the new polarization are opposed to the previous one. The resulting Debye-like relaxation frequency depends on the sample thickness. 

The rotational diffusion constant and relaxation frequency depend on temperature mainly through the temperature dependence of the viscosity which... 

Figure C3.5.10. Frequency-dependent vibronic relaxation data for pentacene (PTC) in naphthalene (N) crystals at 1.5 K. (a) Vibrational echoes are used to measure VER lifetimes (from [99]). The lifetimes are shorter in regime I, longer in regime II, and become shorter again in regime III. (b) Two-colour pump-probe experiments are used to measure vibrational cooling (return to the ground state) from [1021.

Ionic liquids, however, are often quite viscous, and the measurements are thus beyond the extreme narrowing region. The relaxation rates hence become frequency-dependent. Under these conditions, the equation for the spin-lattice relaxation rate becomes more complex ... 

Dielectric measurements were used to evaluate the degrees of inter- and intramolecular hydrogen bonding in novolac resins.39 The frequency dependence of complex permittivity (s ) within a relaxation region can be described with a Havriliak and Negami function (HN function) ... 

Some information concerning the intramolecular relaxation of the hyperbranched polymers can be obtained from an analysis of the viscoelastic characteristics within the range between the segmental and the terminal relaxation times. In contrast to the behavior of melts with linear chains, in the case of hyperbranched polymers, the range between the distinguished local and terminal relaxations can be characterized by the values of G and G" changing nearly in parallel and by the viscosity variation having a frequency with a considerably different exponent 0. This can be considered as an indication of the extremely broad spectrum of internal relaxations in these macromolecules. To illustrate this effect, the frequency dependences of the complex viscosities for both linear... 

As discussed in Sect. 6.2, the electronic states of a paramagnetic ion are determined by the spin Hamiltonian, (6.1). At finite temperamres, the crystal field is modulated because of thermal oscillations of the ligands. This results in spin-lattice relaxation, i.e. transitions between the electronic eigenstates induced by interactions between the ionic spin and the phonons [10, 11, 31, 32]. The spin-lattice relaxation frequency increases with increasing temperature because of the temperature dependence of the population of the phonon states. For high-spin Fe ", the coupling between the spin and the lattice is weak because of the spherical symmetry of the ground state. This... 

Under potentiostatic conditions, the photocurrent dynamics is not only determined by faradaic elements, but also by double layer relaxation. A simplified equivalent circuit for the liquid-liquid junction under illumination at a constant DC potential is shown in Fig. 18. The difference between this case and the one shown in Fig. 7 arises from the type of perturbation introduced to the interface. For impedance measurements, a modulated potential is superimposed on the DC polarization, which induces periodic responses in connection with the ET reaction as well as transfer of the supporting electrolyte. In principle, periodic light intensity perturbations at constant potential do not affect the transfer behavior of the supporting electrolyte, therefore this element does not contribute to the frequency-dependent photocurrent. As further clarified later, the photoinduced ET... 

Fig. 1.24 Two examples of frequency-depen-dent relaxation times - 7"i is plotted as a function of the proton resonance frequency V = ou/2 JI, which was obtained from measurements at different magnetic fields strengths. Left polyisoprene (PI) melts and solutions of the same samples at 19wt-% concentration in cyclohexane. Numbers indicate the average molecular weight. The difference between the melt and solution increases towards lower magnetic fields strengths, the frequency dependence is more pronounced for melts.

In the case of dynamic mechanical relaxation the Zimm model leads to a specific frequency ( ) dependence of the storage [G ( )] and loss [G"(cd)] part of the intrinsic shear modulus [G ( )] [1]. The smallest relaxation rate l/xz [see Eq. (80)], which determines the position of the log G (oi) and log G"(o>) curves on the logarithmic -scale relates to 2Z(Q), if R3/xz is compared with Q(Q)/Q3. The experimental results from dilute PDMS and PS solutions under -conditions [113,114] fit perfectly to the theoretically predicted line shape of the components of the modulus. In addition l/xz is in complete agreement with the theoretical prediction based on the pre-averaged Oseen tensor. 

The relaxation of the fluorescence spectrum takes place as a result of rearrangement of all molecules in solvate (with characteristic times of orientational relaxation) and depends essentially on the exciting radiation frequency, that is, on the type of selectively excited solvates. The following three characteristic cases are possible ... 

Relation [1] Is the frequency-dependent analogue of a formula proposed by Chasset and Thirion (2, 3) which has since been applied very frequently to relaxation measurements on cured rubbers. The next three equations are Inspired by similar relations In dielectrics (they are not derived from these) Equation [2] by the Cole-Cole and Equation [3] by the Davidson-Cole relation (15, 16). Both are special cases of the most general Equation [4] which contains five parameters (17). 

Summary. Coherent optical phonons are the lattice atoms vibrating in phase with each other over a macroscopic spatial region. With sub-10 fs laser pulses, one can impulsively excite the coherent phonons of a frequency up to 50THz, and detect them optically as a periodic modulation of electric susceptibility. The generation and relaxation processes depend critically on the coupling of the phonon mode to photoexcited electrons. Real-time observation of coherent phonons can thus offer crucial insight into the dynamic nature of the coupling, especially in extremely nonequilibrium conditions under intense photoexcitation. 

The equilibrium constant and dissociation rate constant were determined simultaneously by non-linear least-squares fitting, unless the absorption signal was too low157 or no dependence of relaxation frequency on concentration was observed.159,161,162 The association rate constant was then calculated from the definition of the equilibrium constant. The equilibrium constants determined from the dynamics in this manner agree fairly well with equilibrium constants determined independently. 

---