Solvent relaxation rate

Investigation of water motion in AOT reverse micelles determining the solvent correlation function, C i), was first reported by Sarkar et al. [29]. They obtained time-resolved fluorescence measurements of C480 in an AOT reverse micellar solution with time resolution of > 50 ps and observed solvent relaxation rates with time constants ranging from 1.7 to 12 ns. They also attributed these dynamical changes to relaxation processes of water molecules in various environments of the water pool. In a similar study investigating the deuterium isotope effect on solvent motion in AOT reverse micelles. Das et al. [37] reported that the solvation dynamics of D2O is 1.5 times slower than H2O motion. 

Many systems are in an intermediate regime, i.e., xm Tim- In those cases, the measured paramagnetic enhancement of the solvent relaxation rate is given by (Eq. (2) of Chapter 2) ... 

Molecular hydration in solution is described not only by the inner-sphere water molecules (first and second coordination spheres, see Section II.A.l) but also by solvent water molecules freely diffusing up to a distance of closest approach to the metal ion, d. The latter molecules are responsible for the so-called outer-sphere relaxation (83,84), which must be added to the paramagnetic enhancement of the solvent relaxation rates due to inner-sphere protons to obtain the total relaxation rate enhancement,... 

Complementing the equilibrium measurements will be a series of time resolved studies. Dynamics experiments will measure solvent relaxation rates around chromophores adsorbed to different solid-liquid interfaces. Interfacial solvation dynamics will be compared to their bulk solution limits, and efforts to correlate the polar order found at liquid surfaces with interfacial mobility will be made. Experiments will test existing theories about surface solvation at hydrophobic and hydrophilic boundaries as well as recent models of dielectric friction at interfaces. Of particular interest is whether or not strong dipole-dipole forces at surfaces induce solid-like structure in an adjacent solvent. If so, then these interactions will have profound effects on interpretations of interfacial surface chemistry and relaxation. 

The relaxation of solvent nuclei around a paramagnetic centre has been described by Solomon, Bloembergen and others [3-8]. The observed solvent relaxation rate, 1/T, obs, is the sum of a diamagnetic term l/Tid, corresponding to the relaxation rate of the solvent nuclei without the paramagnetic solute, and a paramagnetic term 1/T, p which is the relaxation rate enhancement caused by the paramagnetic substance ... 

Simulations of solvation dynamics following charge transfer at the water liquid/vapor interface[53,80] have shown that the solvent relaxation rate is quite close to that in bulk water, even though one might expect (based on the reduced interfacial dielectric constant and simple continuum model arguments) to have a significantly slower relaxation rate. The reason for this behavior is that the interface is deformed and the ion is able to keep its first solvation shell nearly intact. Since a major part of the solvation dynamics is due to the reorientation of first shell solvent dipoles, the rate relative to the bulk is not altered by much. 

There are two separate contributions to the solvent relaxation rate that are introduced by the presence of solute protein, both of which add to the field-independent relaxation rate of protons in pure solvent the larger NMRD contribution, labelled A, disperses at low fields with an inflection generally between 0.1 and 10 MHz the smaller contribution, labelled D, is known to... 

Solvent relaxation rates are only likely to provide information about ionisation in the circumstances where either,... 

Relaxation studies yield information about the overall solvent dynamics, which in some cases can be difficult to interpret, as contributions to the solvent relaxation rate arise from various origins, such as changes in surface hydration, polymer hydration, coagulation, conformational changes which might lead to water release on adsorption. Additional contributions to the relaxation rate can arise from changes of the degree of dissociation, from cross-relaxation in... 

Summarizing, it may be concluded that NMR relaxation studies promise to yield quite interesting and useful results in the field of the physics of polyelectrolyte solutions. Problems that should be resolved in the near future concern the relative importance of the ionic and the solvent contributions to the relaxation rate. Investigation of the solvent relaxation rate may be of use here. The validity of neglecting the reorientation of the rod in the tentative theoretical description of the counter-ion relaxation can perhaps be checked on oriented systems or in ion exchangers. Diffusion coefficients for the counter-ions in these systems, determined by NMR, should be a very important help in understanding the physical properties of polyelectrolyte solutions. 

Chandra and his coworkers have developed analytical theories to predict and explain the interfacial solvation dynamics. For example, Chandra et al. [61] have developed a time-dependent density functional theory to predict polarization relaxation at the solid-liquid interface. They find that the interfacial molecules relax more slowly than does the bulk and that the rate of relaxation changes nonmonotonically with distance from the interface They attribute the changing relaxation rate to the presence of distinct solvent layers at the interface. Senapati and Chandra have applied theories of solvents at interfaces to a range of model systems [62-64]. 

Although many different processes can control the observed swelling kinetics, in most cases the rate at which the network expands in response to the penetration of the solvent is rate-controlling. This response can be dominated by either diffu-sional or relaxational processes. The random Brownian motion of solvent molecules and polymer chains down their chemical potential gradients causes diffusion of the solvent into the polymer and simultaneous migration of the polymer chains into the solvent. This is a mutual diffusion process, involving motion of both the polymer chains and solvent. Thus the observed mutual diffusion coefficient for this process is a property of both the polymer and the solvent. The relaxational processes are related to the response of the polymer to the stresses imposed upon it by the invading solvent molecules. This relaxation rate can be related to the viscoelastic properties of the dry polymer and the plasticization efficiency of the solvent [128,129],... 

A comparison with Burchard s first cumulant calculations shows qualitative agreement, in particular with respect to the position of the minimum. Quantitatively, however, important differences are obvious. Both the sharpness as well as the amplitude of the phenomenon are underestimated. These deviations may originate from an overestimation of the hydrodynamic interaction between segments. Since a star of high f internally compromises a semi-dilute solution, the back-flow field of solvent molecules will be partly screened [40,117]. Thus, the effects of hydrodynamic interaction, which in general eases the renormalization effects owing to S(Q) [152], are expected to be weaker than assumed in the cumulant calculations and thus the minimum should be more pronounced than calculated. Furthermore, since for Gaussian chains the relaxation rate decreases... 

Fig. 58a, b. Segmental diffusion in semi-dilute polymer solutions. Schematic view of the Q-dependence of the relaxation rates Q(Q) at a fixed concentration. a Good solvent conditions b -conditions. (Reprinted with permission from [168]. Copyright 1994... 

Fig. 63. PDMS/d-bromobenzene at 357 K (0-solvent system). Reduced relaxation rate Q(Q) of the segmental dynamics as dependent on Q for various concentrations. (Reprinted with permission from [168]. Copyright 1994 Elsevier Science B.V., Amsterdam)...

Molecular rotors are useful as reporters of their microenvironment, because their fluorescence emission allows to probe TICT formation and solvent interaction. Measurements are possible through steady-state spectroscopy and time-resolved spectroscopy. Three primary effects were identified in Sect. 2, namely, the solvent-dependent reorientation rate, the solvent-dependent quantum yield (which directly links to the reorientation rate), and the solvatochromic shift. Most commonly, molecular rotors exhibit a change in quantum yield as a consequence of nonradia-tive relaxation. Therefore, the fluorophore s quantum yield needs to be determined as accurately as possible. In steady-state spectroscopy, emission intensity can be calibrated with quantum yield standards. Alternatively, relative changes in emission intensity can be used, because the ratio of two intensities is identical to the ratio of the corresponding quantum yields if the fluid optical properties remain constant. For molecular rotors with nonradiative relaxation, the calibrated measurement of the quantum yield allows to approximately compute the rotational relaxation rate kor from the measured quantum yield [Pg.284]

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