Thermodynamic lengths and intrinsic time scales in molecular relaxation

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Abstract
A connection is made between a thermodynamic length defined on the full space of statistical mechanical states and dissipation (entropy produced) in any irreversible process undergone by a system interacting with an environment which is in equilibrium. Vibrational and rotational relaxation are studied for the two cases when the environment has a fixed temperature and when its temperature varies with time. The metric lower bound on entropy produced is found to be excellent. The variation of the instantaneous relaxation time of these microscopic systems is contrasted with the behavior of a macroscopic conjugate-linear (Onsager-type) system.

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