Advances in Chemical Physics, Vol.140 (Wiley 2008) by Stuart A. Rice

By Stuart A. Rice

This sequence presents the chemical physics box with a discussion board for severe, authoritative reviews of advances in each zone of the self-discipline.

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Even when the subsystem force is nonlinear, the reservoir force remains independent of x. The analysis will be carried out using the nonlinear results for the subsystem; in the linear regime the correspondence given in the preceding subsection can be applied. The second entropy then is a function of three constrained variables, Sð2Þ ðÁ0 x; Ár x; xjt; Xr Þ. The internal part, which accounts for the resistance to the flux, is as given earlier; it characterizes the transition x ! x0 . The external part is entirely influenced by the reservoir, and it consists of two parts: the equilibration with the reservoir for the initial state x, and the transition x0 !

They show that the magnitude of the coupling coefficient between a flux and a force is equal to that between the force and the flux. 1. Asymmetry of the Transport Matrix A significant question is whether the asymmetric contribution to the transport matrix is zero or nonzero. That is, is there any coupling between the transport of variables of opposite parity? The question will recur in the discussion of the rate of entropy production later. The earlier analysis cannot decide the issue, since b3 can be zero or nonzero in the earlier results.

Take, for example, the case of a subsystem with mobile charges on which is imposed crossed electric and magnetic fields. A steady current flows in the direction of the electric field, and an internal voltage is induced transverse to the electric field such that there is no net transverse force or flux (Hall effect). The induced transverse force is not equal to the imposed magnetic force (but it is equal and opposite to the induced Lorentz force), and hence the earlier result for the average internal force equalling the imposed force no longer holds.

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