No abstract

An exact equation for the matrix elements of the system of moments [the expectation values of the spherical harmonics ͗Y n,m ͘ ͑t͒], which govern the kinetics of the magnetization M of a single domain particle, is derived. This derivation is based on the representation of the stochastic Gilbert equation augmented by a random field and the corresponding Fokker-Planck equation for the distribution function of the orientations of M in terms of the angular momentum operators and on the subsequent evaluation of the matrix elements in terms of the Clebsch-Gordan coefficients. [S0031-9007(99)08847-X]

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The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ0 = ℏω0/k(B)T where ω0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ0 < 1 - 3) and for low (ξ0 ≫ 1) temperature ranges. For the first (quasi-classical) kinetic regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T → 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the existing theories of the ET. Our alternative dynamic ET model for local modes immersed in the continuum harmonic medium is formulated for both classical and quantum regimes, and accounts explicitly for the mode∕medium interaction. The kinetics of the energy exchange between the local ET subsystem and the surrounding environment essentially determine the total ET rate. The efficient computer code for rate computations is elaborated on. The computations are available for a wide range of system parameters, such as the temperature, external field, local mode frequency, and characteristics of mode/medium interaction. The relation of the present approach to the Marcus ET theory and to the quantum-statistical reaction rate theory [V. G. Levich and R. R. Dogonadze, Dokl. Akad. Nauk SSSR, Ser. Fiz. Khim. 124, 213 (1959); J. Ulstrup, Charge Transfer in Condensed Media (Springer, Berlin, 1979); M. Bixon and J. Jortner, Adv. Chem. Phys. 106, 35 (1999)] underlying it is discussed and illustrated by the results of computations for practically important target...

The magnetic relaxation of single-domain ferromagnetic particles with cubic magnetic anisotropy is treated by averaging the Gilbert-Langevin equation for an individual particle, so that the system of linear differentialrecurrence relations for the appropriate equilibrium correlation functions is derived without recourse to the Fokker-Planck equation. The solution of this system ͑in terms of matrix continued fractions͒ is determined and the longitudinal relaxation time and spectrum of the complex magnetic susceptibility are evaluated. It is shown that in contrast to particles with uniaxial anisotropy, there is an inherent geometric dependence of the complex susceptibility and the relaxation time on the damping parameter arising from coupling of longitudinal and transverse relaxation modes. ͓S0163-1829͑98͒06829-5͔

The infinite hierarchy of differential-recurrence relations for ensemble averages of the spherical harmonics pertaining to the noninertial rotational Brownian motion of an ensemble of polar and anisotropically polarizable molecules in a strong external dc electric field is derived by averaging the underlying Langevin equation. This procedure avoids recourse to the Fokker-Planck equation, the solution of which involves complicated mathematical manipulations. Exact analytic solutions for the spectra of the relaxation functions and relaxation times for nonlinear dielectric relaxation and dynamic Kerr effect of symmetric top molecules are calculated for two limiting cases, namely, pure induced dipole moments and pure permanent moments, using the continued fraction method. The general case where both types of moment are taken into account is then considered by using matrix continued fractions. Exact expressions for the dielectric and Kerr effect relaxation times are also derived as functions of the parameters and characterizing the field-off and the induced dipole moments. Plots of these relaxation times are presented for various values of and . The nonlinear relaxation behavior is emphasized in figures showing how the real and imaginary parts of the spectra of the relaxation functions deviate from the Lorentzian profiles.

The itinerant oscillator model describing rotation of a dipole about a fixed axis inside a cage formed by its surrounding polar molecules is revisited in the context of modeling the dielectric relaxation of a polar fluid via the Langevin equation. The dynamical properties of the model are studied by averaging the Langevin equations describing the complex orientational dynamics of two bodies (molecule-cage) over their realizations in phase space so that the problem reduces to solving a system of three index linear differential-recurrence relations for the statistical moments. These are then solved in the frequency domain using matrix continued fractions. The linear dielectric response is then evaluated for extensive ranges of damping, dipole moment ratio, and cage-dipole inertia ratio and along with the usual inertia corrected microwave Debye absorption gives rise to significant far-infrared absorption with a comb-like structure of harmonic peaks. The model may be also regarded as an extension of Budó's [J. Chem. Phys. 17, 686 (1949)] treatment of molecules containing rotating polar groups to include inertial effects.

The nonlinear transient response of polar and polarizable particles (macromolecules) diluted in a nonpolar solvent to a sudden change both in magnitude and in direction of a strong external dc field is considered. By averaging the underlying Langevin equation, the infinite hierarchy of differential-recurrence equations for ensemble averages of the spherical harmonics is derived for an assembly of polar and anisotropically polarizable molecules pertaining to the noninertial rotational Brownian motion. On solving this hierarchy, the relaxation functions and relaxation times appropriate to the transient dynamic Kerr effect and nonlinear dielectric relaxation are calculated. The calculations are accomplished using the matrix continued fraction method, which allows us to express exactly the solution of the infinite hierarchy of differential-recurrence relations for the first- and second-order transient responses of the ensemble averages of the spherical harmonics (relaxation functions). The results are then compared with available experimental data and solutions previously obtained for various particular cases.