Relaxation external fields

So long as the field is on, these populations continue to change however, once the external field is turned off, these populations remain constant (discounting relaxation processes, which will be introduced below). Yet the amplitudes in the states i and i / do continue to change with time, due to the accumulation of time-dependent phase factors during the field-free evolution. We can obtain a convenient separation of the time-dependent and the time-mdependent quantities by defining a density matrix, p. For the case of the wavefiinction ), p is given as the outer product of v i) with itself. 

The second equality is obtained using the fomi of the external field r Jspecific to the relaxation... 

The dielectric constant (permittivity) tabulated is the relative dielectric constant, which is the ratio of the actual electric displacement to the electric field strength when an external field is applied to the substance, which is the ratio of the actual dielectric constant to the dielectric constant of a vacuum. The table gives the static dielectric constant e, measured in static fields or at relatively low frequencies where no relaxation effects occur. 

For simple outer-sphere electron transfer reactions, the effective frequency co is determined by the properties of the slow polarization of the medium. For a liquid like water, where the temporal relaxation of the slow polarization as a response to the external field is single exponential, tfie effective frequency is equal to... 

Fig. 9.24 Theoretical calculations of nuclear forward scattering for the relaxation rates as indicated for a system with electron spin S = 1/2, hyperfine parameters A y jg fi = 50 T, and AF.q = 2 mm s in an external field of 75 mT applied perpendicular to k and O . The transition probabilities co in ((9.8a) and (9.8b)) are expressed in units of mm s , with 1 mm corresponding to 7.3 10 s. (Taken Ifom [30])...

In the ideal case, the ionic conductivity is given by the product z,Ft/ . Because of the electrophoretic effect, the real ionic mobility differs from the ideal by A[/, and equals U° + At/,. Further, in real systems the electric field is not given by the external field E alone, but also by the relaxation field AE, and thus equals E + AE. Thus the conductivity (related to the unit external field E) is increased by the factor E + AE)/E. Consideration of both these effects leads to the following expressions for the equivalent ionic conductivity (cf. Eq. 2.4.9) ... 

Mozumder (1969b) pointed out that in the presence of freshly created charges due to ionization, the dielectric relaxes faster—with the longitudinal relaxation time tl, rather than with the usual Debye relaxation time T applicable for weak external fields. The evolution of the medium dielectric constant is then given by... 

Equation (10.6) for the mobility in the two-state model implicitly assumes that the electron lifetime in the quasi-free state is much greater than the velocity relaxation (or autocorrelation) time, so that a stationary drift velocity can occur in the quasi-free state in the presence of an external field. This point was first raised by Schmidt (1977), but no modification of the two-state model was proposed until recently. Mozumder (1993) introduced the quasi-ballistic model to correct for the competition between trapping and velocity randomization in the quasi-free state. 

Figure 10.2 Arrhenius plot of the natural logarithm of the relaxation time extracted from the ac susceptibility data as a function of the inverse temperature for 1 at different external fields as indicated. (Reprinted from Ref. [6]. Copyright (2009) American Chemical Society.)...

A quantitative evaluation of the relaxivities as a function of the magnetic field Bo requires extensive numerical calculations because of the presence of two different axes (the anisotropy and the external field axis), resulting in non-zero off-diagonal elements in the Hamiltonian matrix (15). Furthermore, the anisotropy energy has to be included in the thermal equilibrium density matrix. Figures 7 and 8 show the attenuation of the low field dispersion of the calculated NMRD profile when either the crystal size or the anisotropy field increases. 

The relaxation rates calculated from Eq. (15) are smaller than the measured ones at low field, while they are larger at high field. OST is thus obviously unable to match the experimental results. However, water protons actually diffuse around ferrihydrite and akaganeite particles and there is no reason to believe that the contribution to the rate from this diffusion would not be quadratic with the external field. This contribution is not observed, probably because the coefficient of the quadratic dependence with the field is smaller than predicted. This could be explained by an erroneous definition of the correlation length in OST, this length is the particle radius, whilst the right definition should be the mean distance between random defects of the crystal. This correlation time would then be significantly reduced, hence the contribution to the relaxation rate. 

In a traditional magnet for NMR spectroscopy, the field Bq of the magnet is much higher than the field components originating from outside sources. Moreover, devices such as efficient NMR field stabilizers are used to suppress all interfering external fields. Consequently, the presence of such field components can be usually ignored. On the contrary, during a FFC NMR measurement the sample may be subject to very low fields (ideally down to zero) which is practically impossible when the relaxation field value becomes comparable to the environmental fields. The amplitude of such fields, if not compensated, represents the lower relaxation field limit for a reliable NMRD profile. 

Nevertheless, calculation of such properties as spin-dependent electronic densities near nuclei, hyperfine constants, P,T-parity nonconservation effects, chemical shifts etc. with the help of the two-component pseudospinors smoothed in cores is impossible. We should notice, however, that the above core properties (and the majority of other properties of practical interest which are described by the operators heavily concentrated within inner cores or on nuclei) are mainly determined by electronic densities of the valence and outer core shells near to, or on, nuclei. The valence shells can be open or easily perturbed by external fields, chemical bonding etc., whereas outer core shells are noticeably polarized (relaxed) in contrast to the inner core shells. Therefore, accurate calculation of electronic structure in the valence and outer core region is of primary interest for such properties. 

Dipolar ions like CN and OH can be incorporated into solids like NaCl and KCl. Several small dopant ions like Cu and Li ions get stabilized in off-centre positions (slightly away from the lattice positions) in host lattices like KCl, giving rise to dipoles. These dipoles, which are present in the field of the crystal potential, are both polarizable and orientable in an external field, hence the name paraelectric impurities. Molecular ions like SJ, SeJ, Nf and O J can also be incorporated into alkali halides. Their optical spectra and relaxation behaviour are of diagnostic value in studying the host lattices. These impurities are characterized by an electric dipole vector and an elastic dipole tensor. The dipole moments and the orientation direction of a variety of paraelectric impurities have been studied in recent years. The reorientation movements may be classical or involve quantum-mechanical tunnelling. 

Because the charged particle and its ion atmosphere move in opposite directions, the center of positive charge and the center of negative charge do not coincide. If the external field is removed, this asymmetry disappears over a period of time known as the relaxation time. Therefore, in addition to the fact that the colloid and its atmosphere move countercurrent with respect to one another (which is called the retardation effect), there is a second inhibiting effect on the migration that arises from the tug exerted on the particle by its distorted atmosphere. Retardation and relaxation both originate with the double layer, then, but describe two different consequences of the ion atmosphere. The theories we have discussed until now have all correctly incorporated retardation, but relaxation effects have not been included in any of the models considered so far. 

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