Relaxation shape

The tense and relaxed forms of a-cyclodextrin mimic the induced-fit model proposed for enzymes. In the inclusion complexes of a-cyclodextrin, the macrocycle adopts a round, relaxed shape with all the 0(2),0(3) hydroxyls engaged in intramolecular 0(2)- (3 ) hydrogen bonds (Fig. 18.8) [577]. The average O - - O distance of around 3.0 A is consistent with an H 0 separation of about 2.0 A, indicating relatively weak interactions. This form of a-cyclodextrin persists even when an included guest molecule, such as krypton (3.8 A diameter) is too small to fully occupy the 5.0 A cavity and is disordered over several sites [578], analogous to the gas hydrate structures discussed in Part IV, Chapter 21. 

Salol is another system for which the invariance under pressure of the a-relaxation shape was reported. Recent PCS experiments [125,126] revealed that the correlation functions acquired at different pressures up to 180 MPa and at room temperature superposed. The stretching parameter >KWW was 0.68, in agreement with the PCS measurements done at ambient pressure [127,128]. 

From SCRP spectra one can always identify the sign of the exchange or dipolar interaction by direct exammation of the phase of the polarization. Often it is possible to quantify the absolute magnitude of D or J by computer simulation. The shape of SCRP spectra are very sensitive to dynamics, so temperature and viscosity dependencies are infonnative when knowledge of relaxation rates of competition between RPM and SCRP mechanisms is desired. Much use of SCRP theory has been made in the field of photosynthesis, where stnicture/fiinction relationships in reaction centres have been connected to their spin physics in considerable detail [, Mj. 

The scan rate, u = EIAt, plays a very important role in sweep voltannnetry as it defines the time scale of the experiment and is typically in the range 5 mV s to 100 V s for nonnal macroelectrodes, although sweep rates of 10 V s are possible with microelectrodes (see later). The short time scales in which the experiments are carried out are the cause for the prevalence of non-steady-state diflfiision and the peak-shaped response. Wlien the scan rate is slow enough to maintain steady-state diflfiision, the concentration profiles with time are linear within the Nemst diflfiision layer which is fixed by natural convection, and the current-potential response reaches a plateau steady-state current. On reducing the time scale, the diflfiision layer caimot relax to its equilibrium state, the diffusion layer is thiimer and hence the currents in the non-steady-state will be higher. 

Loring R F, Van Y J and Mukamel S 1987 Time-resolved fluorescence and hole-burning line shapes of solvated molecules longitudinal dielectric relaxation and vibrational dynamics J. Chem. Phys. 87 5840-57... 

Another aspect of plasticity is the time dependent progressive deformation under constant load, known as creep. This process occurs when a fiber is loaded above the yield value and continues over several logarithmic decades of time. The extension under fixed load, or creep, is analogous to the relaxation of stress under fixed extension. Stress relaxation is the process whereby the stress that is generated as a result of a deformation is dissipated as a function of time. Both of these time dependent processes are reflections of plastic flow resulting from various molecular motions in the fiber. As a direct consequence of creep and stress relaxation, the shape of a stress—strain curve is in many cases strongly dependent on the rate of deformation, as is illustrated in Figure 6. 

This effect of concentration is particularly pronounced with irregularly shaped particles. A possible explanation of the variation in the specific resistance is in terms of the time available for the particles to orient themselves in the growing cake. At higher concentrations, but with the same approach velocities, less time, referred to as particle relaxation time, is available for a stable cake to form and a low resistance results. 

When q is zero, Eq. (5-18) reduces to the famihar Laplace equation. The analytical solution of Eq. (10-18) as well as of Laplaces equation is possible for only a few boundary conditions and geometric shapes. Carslaw and Jaeger Conduction of Heat in Solids, Clarendon Press, Oxford, 1959) have presented a large number of analytical solutions of differential equations apphcable to heat-conduction problems. Generally, graphical or numerical finite-difference methods are most frequently used. Other numerical and relaxation methods may be found in the general references in the Introduction. The methods may also be extended to three-dimensional problems. 

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