Dynamic anisotropy dependence

During the course of these and related studies, notably those concerned with the temperature dependence of the mechanical anisotropy and the identification of relaxation processes in structural terms, it became apparent that the aggregate model was successful in low density polyethylene because it described effectively the influence of the very anisotropic x-relaxation process on the mechanical behaviour. Stachurski and Ward were even able to extend the aggregate model to deal with the anisotropy of dynamic loss factor. (See Chapter 9 for further discussion.) It was, however, more in the spirit of the original conception of the aggregate model that it would deal with mechanical anisotropy in glassy polymers, where morphology was of secondary importance. 

From the dynamic point of view, as illustrated in Fig. 4.3, polymer coUs are rather ellipsoids with their anisotropy depending upon chain semi-flexibility, and their hydrodynamic radii are usually larger than their radii of gyration. Thus, a dynamic overlap concentration C < C exists, which is of practical importance for characterizing the hydrodynamic property of the polymers in solutimis. 

As highlighted in Equation (5.5), the polarization anisotropy depends on the light wavelength, and can vary over time, and thus is a very sensitive probe of energy excitation migrations in the nanostructures. For example, for MEH-PPV/silica membrane composite systems one finds values of about 4.5 and below 1 for pp z and pp x, respectively. In addition, the temporal dynamics of... 

In linear, spherical and synnnetric tops the components of a along and perpendicular to the principal axis of synnnetry are often denoted by a and respectively. In such cases, the anisotropy is simply Aa = tty -If the applied field is oscillating at a frequency w, then the dipole polarizability is frequency dependent as well a(co). The zero frequency limit of the dynamic polarizability a(oi) is the static polarizability described above. 

This method has been devised as an effective numerical teclmique of computational fluid dynamics. The basic variables are the time-dependent probability distributions f x, f) of a velocity class a on a lattice site x. This probability distribution is then updated in discrete time steps using a detenninistic local rule. A carefiil choice of the lattice and the set of velocity vectors minimizes the effects of lattice anisotropy. This scheme has recently been applied to study the fomiation of lamellar phases in amphiphilic systems [92, 93]. 

Surface SHG [4.307] produces frequency-doubled radiation from a single pulsed laser beam. Intensity, polarization dependence, and rotational anisotropy of the SHG provide information about the surface concentration and orientation of adsorbed molecules and on the symmetry of surface structures. SHG has been successfully used for analysis of adsorption kinetics and ordering effects at surfaces and interfaces, reconstruction of solid surfaces and other surface phase transitions, and potential-induced phenomena at electrode surfaces. For example, orientation measurements were used to probe the intermolecular structure at air-methanol, air-water, and alkane-water interfaces and within mono- and multilayer molecular films. Time-resolved investigations have revealed the orientational dynamics at liquid-liquid, liquid-solid, liquid-air, and air-solid interfaces [4.307]. 

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. 

NMR spectroscopy is a powerful technique to study molecular structure, order, and dynamics. Because of the anisotropy of the interactions of nuclear spins with each other and with their environment via dipolar, chemical shift, and quadrupolar interactions, the NMR frequencies depend on the orientation of a given molecular unit relative to the external magnetic field. NMR spectroscopy is thus quite valuable to characterize partially oriented systems. Solid-state NMR... 

When r s, one has interconversion between operators Br and Bs, and Rrs is a cross-relaxation rate. Note that the cross-relaxation may or may not contain interference effects depending on the indices l and /, which keep track of interactions Cyj and C,. Cross-correlation rates and cross-relaxation rates have not been fully utilized in LC. However, there is a recent report41 on this subject using both the 13C chemical shielding anisotropy and C-H dipolar coupling relaxation mechanisms to study a nematic, and this may be a fruitful arena in gaining dynamic information for LC. We summarize below some well known (auto-)relaxation rates for various spin interactions commonly encountered in LC studies. 

Finally, it should be noted that homo-FRET, which is just the exchange of energies between the same dyes, is undetected by common spectroscopic or lifetime measurements and needs the hetero-FRET probing for its detection. The Red-Edge effect allows the easy distinguishing of the decrease of anisotropy due to FRET (static effect) from that occurring due to rotational freedom of fluorophores (dynamic effect), which does not depend on excitation wavelength. 

The major reasons for using intrinsic fluorescence and phosphorescence to study conformation are that these spectroscopies are extremely sensitive, they provide many specific parameters to correlate with physical structure, and they cover a wide time range, from picoseconds to seconds, which allows the study of a variety of different processes. The time scale of tyrosine fluorescence extends from picoseconds to a few nanoseconds, which is a good time window to obtain information about rotational diffusion, intermolecular association reactions, and conformational relaxation in the presence and absence of cofactors and substrates. Moreover, the time dependence of the fluorescence intensity and anisotropy decay can be used to test predictions from molecular dynamics.(167) In using tyrosine to study the dynamics of protein structure, it is particularly important that we begin to understand the basis for the anisotropy decay of tyrosine in terms of the potential motions of the phenol ring.(221) For example, the frequency of flips about the C -C bond of tyrosine appears to cover a time range from milliseconds to nanoseconds.(222)... 

The final rotational state distributions of the products in the fragmentation of a polyatomic molecule contain additional clues about the intra- and intermolecular dynamics, especially about the coupling in the exit channel. In realistic as well as model studies it has been observed that the rotational state distributions of the photodissociation products reflect the angular dependence of the wave function at the transition state and the anisotropy of the PES in the exit channel [4, 9, 10]. HO2 is no exception. 

Reticulum ATPase [105,106], Owing to the long-lived nature of the triplet state, Eosin derivatives are suitable to study protein dynamics in the microsecond-millisecond range. Rotational correlation times are obtained by monitoring the time-dependent anisotropy of the probe s phosphorescence [107-112] and/or the recovery of the ground state absorption [113— 118] or fluorescence [119-122], The decay of the anisotropy allows determination of the mobility of the protein chain that cover the binding site and the rotational diffusion of the protein, the latter being a function of the size and shape of the protein, the viscosity of the medium, and the temperature. 

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