Closed form solution of the itinerant oscillator model of molecular libration

It is shown by using self-consistent (so that action and reaction torques are fully accounted for) expressions for the viscous drag and white noise terms in the equations of motion of the fixed axis rotator version of the itinerant oscillator model that the characteristic (secular) equation of the system automatically factorizes. Hence all the correlation functions of the model (which consists of a ''cage'' of dipolar molecules surrounding a tagged molecule) may be given in closed form. In particular, the orientational correlation functions of the tagged molecule become the products of single particle ones namely those of a free Brownian rotator and a damped harmonic oscillator while the orientational correlation functions of the cage are simply those of the free Brownian rotator, The equations of motion of the system likewise decouple when the restrictions of small oscillations and of rotation about a fixed axis are removed. Thus, irrespective of the form of the interaction potential between the cage and the tagged molecule, the relaxation modes of the system separate into those of the tagged molecule and those of its surroundings which behave as an inertia corrected free Brownian rotator. (C) 1997 American Institute of Physics.