Librational spectral function model

Using the so-called planar libration-regular precession (PL-RP) approximation, it is possible to reduce the double integral for the spectral function to a simple integral. The interval of integration is divided in the latter by two intervals, and in each one the integrands are substantially simplified. This simplification is shown to hold, if a qualitative absorption frequency dependence should be obtained. Useful simple formulas are derived for a few statistical parameters of the model expressed in terms of the cone angle (5 and of the lifetime x. A small (3 approximation is also considered, which presents a basis for the hybrid model. The latter is employed in Sections IV and VIII, as well as in other publications (VIG). 

In the second period, which was ended by review GT after the average perturbation theorem was proved, it became possible to get the Kubo-like expression for the spectral function L(z) (GT, p. 150). This expression is applicable to any axially symmetric potential well. Several collision models were also considered, and the susceptibility was expressed through the same spectral function L(z) (GT, p. 188). The law of motion of the particles should now be determined only by the steady state. So, calculations became much simpler than in the period (1). The best achievements of the period (2) concern the cone-confined rotator model (GT, p. 231), in which the dipoles were assumed to librate in space in an infinitely deep rectangular well, and applications of the theory to nonassociated liquids (GT, p. 329). 

Equation 37 has been used in an attempt130 to describe internal flexibility of the three hydroxymethyl groups of sucrose molecule in DzO solutions. The experimental data showed that the contribution of the overall motion to the spectral-density function of the hydroxymethyl group is similar to that of the ring carbons of sucrose. However, the presence of rapid internal motions about the three exocyclic bonds reduces the spectral density amplitudes. On the basis of the calculated order parameters in conjunction with model calculations, it was suggested130 that internal motions may be described as torsional librations. 

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