Relaxation rate, temperature dependence

The relaxation rate constants for in PSII membranes containing an intact Sj- or S2-state Mn complex converge as the sample temperature is raised toward 80 K and as the sample temperature falls toward 5 K the maximum enhancement of the relaxation rate in S2-state samples relative to that in Sj-state samples occurs near 10 K (Figure 2). At the high-temperature convergence, the slope of the plot of 1/Ti as a function of temperature for samples with an intact Mn complex is less than that for the model tyrosine system. At the low temperature convergence, the relaxation rate temperature dependence observed for in S2-state samples shows a severe... 

Reorientations produce characteristic maxima in the relaxation rate, which may be different for the various symmetry species of CD4. The measured relaxation rates exhibit dependence on two time constants at low temperatures, but also double maxima for both relaxation rates. We assume that molecules may move over some places (adsorption sites) on the cage walls and experience different local potentials. Under the assumption of large tunnelling splittings the T and (A+E) sub-systems relax at different rates. In the first step of calculation the effect of exchange between the different places was considered. Comparison with experimental data led to the conclusion that we have to include also a new relaxation process, namely the contribution from an external electric field gradient. It is finally quite understandable to expect that such effect appears when CD4 moves in the vicinity of a Na+ ion. 

It is not possible to evaluate k directly, for it appears with the entropy of activation in the temperature-independent part of the rate constant. An estimate of k requires an extrathermodynamic assumption. In two cases of iron(II) spin equilibria examined by ultrasonic relaxation the temperature dependence of the rates was precisely determined. If the assumption is made that all of the entropy of activation is due to a small value of k, minimum values of 10-3 and 10-4 are obtained. Because there is an increase in entropy in the transition from the low-spin to the high-spin states, this assumption is equivalent to assuming that the transition state resembles the high-spin state. There is now evidence that this is not the case. Volumes of activation indicate that the transition state lies about midway between the two spin states. This is a more chemically reasonable and likely situation than the limiting assumption used to evaluate k. In this case the observed entropy of activation includes some chemical contributions which arise from increased solvation and decreased vibrational partition functions as the high-spin state is compressed to the transition state. Consequently, the minimum value of k is increased and is unlikely to be less than about 10 2. 

Most amorphous polymers show, in addition to the dynamic glass transition, a slow p-relaxation. The temperature dependence of its relaxation rate follows an Arrhenius-type equation ... 

Fig. 12 Stress relaxation of Nafion at high and low water activity as a function of temperature. The relaxation rates show inverted trends with water activity at 50°C and 90°C. At 70°C, the relaxation rates cross depending on water activity...

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 occurrence of nonradiative losses is classically illustrated in Figure 3. At sufficiently high temperature the emitting state relaxes to the ground state by the crossover at B of the two curves. In fact, for many broad-band emitting phosphors the temperature dependence of the nonradiative decay rate P is given bv equation 1 ... 

The role of two-phonon processes in the relaxation of tunneling systems has been analyzed by Silbey and Trommsdorf [1990]. Unlike the model of TLS coupled linearly to a harmonic bath (2.39), bilinear coupling to phonons of the form Cijqiqja was considered. In the deformation potential approximation the coupling constant Cij is proportional to (y.cUj. There are two leading two-phonon processes with different dependence of the relaxation rate on temperature and energy gap, A = (A Two-phonon emission prevails at low temperatures, and it is... 

The measurement of correlation times in molten salts and ionic liquids has recently been reviewed [11] (for more recent references refer to Carper et al. [12]). We have measured the spin-lattice relaxation rates l/Tj and nuclear Overhauser factors p in temperature ranges in and outside the extreme narrowing region for the neat ionic liquid [BMIM][PFg], in order to observe the temperature dependence of the spectral density. Subsequently, the models for the description of the reorientation-al dynamics introduced in the theoretical section (Section 4.5.3) were fitted to the experimental relaxation data. The nuclei of the aliphatic chains can be assumed to relax only through the dipolar mechanism. This is in contrast to the aromatic nuclei, which can also relax to some extent through the chemical-shift anisotropy mechanism. The latter mechanism has to be taken into account to fit the models to the experimental relaxation data (cf [1] or [3] for more details). Preliminary results are shown in Figures 4.5-1 and 4.5-2, together with the curves for the fitted functions. 

In molecular doped polymers the variance of the disorder potential that follows from a plot of In p versus T 2 is typically 0.1 eV, comprising contributions from the interaction of a charge carrier with induced as well as with permanent dipoles [64-66]. In molecules that suffer a major structural relaxation after removal or addition of an electron, the polaron contribution to the activation energy has to be taken into account in addition to the (temperature-dependent) disorder effect. In the weak-field limit it gives rise to an extra Boltzmann factor in the expression for p(T). More generally, Marcus-type rates may have to be invoked for the elementary jump process [67]. 

The value of the magnetic hyperfine interaction constant C = 22.00 kHz is supposed to be reliably measured in the molecular beam method [71]. Experimental data for 15N2 are shown in Fig. 1.24, which depicts the density-dependence of T2 = (27tAv1/2)-1 at several temperatures. The fact that the dependences T2(p) are linear until 200 amagat proves that binary estimation of the rotational relaxation rate is valid within these limits and that Eq. (1.124) may be used to estimate cross-section oj from... 

Since the temperatures in question here are so low (1 K and below), we will ignore the energy dependence of (e) in this section and take n(e) = P. In order to see the time dependence of the heat capacity, we obtain the combined distribution of the TLS energy splittings E and relaxation rates —P E, x ),... 

Thus, the starting parameters for the computer-simulation of spectrum IB were chosen to agree with the value of hyperfine fields at 613 K as measured by Rlste and Tenzer, using neutron scattering measurements (36). In addition, the magnetic relaxation rate depends on temperature, as discussed in the Theory section of this paper. 

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