Dynamical randomness, time asymmetry

C. The Chaos-Transport Formula Time Asymmetry in Dynamical Randomness A. Randomness of Fluctuations in NonequiUbrium Steady States... 

The plan of this chapter is the following. Section II gives a summary of the phenomenology of irreversible processes and set up the stage for the results of nonequilibrium statistical mechanics to follow. In Section III, it is explained that time asymmetry is compatible with microreversibility. In Section IV, the concept of Pollicott-Ruelle resonance is presented and shown to break the time-reversal symmetry in the statistical description of the time evolution of nonequilibrium relaxation toward the state of thermodynamic equilibrium. This concept is applied in Section V to the construction of the hydrodynamic modes of diffusion at the microscopic level of description in the phase space of Newton s equations. This framework allows us to derive ab initio entropy production as shown in Section VI. In Section VII, the concept of Pollicott-Ruelle resonance is also used to obtain the different transport coefficients, as well as the rates of various kinetic processes in the framework of the escape-rate theory. The time asymmetry in the dynamical randomness of nonequilibrium systems and the fluctuation theorem for the currents are presented in Section VIII. Conclusions and perspectives in biology are discussed in Section IX. 

This principle and the formula (101) show that entropy production results from a time asymmetry in the dynamical randomness in nonequilibrium steady states. 

It is most remarkable that the entropy production in a nonequilibrium steady state is directly related to the time asymmetry in the dynamical randomness of nonequilibrium fluctuations. The entropy production turns out to be the difference in the amounts of temporal disorder between the backward and forward paths or histories. In nonequilibrium steady states, the temporal disorder of the time reversals is larger than the temporal disorder h of the paths themselves. This is expressed by the principle of temporal ordering, according to which the typical paths are more ordered than their corresponding time reversals in nonequilibrium steady states. This principle is proved with nonequilibrium statistical mechanics and is a corollary of the second law of thermodynamics. Temporal ordering is possible out of equilibrium because of the increase of spatial disorder. There is thus no contradiction with Boltzmann s interpretation of the second law. Contrary to Boltzmann s interpretation, which deals with disorder in space at a fixed time, the principle of temporal ordering is concerned by order or disorder along the time axis, in the sequence of pictures of the nonequilibrium process filmed as a movie. The emphasis of the dynamical aspects is a recent trend that finds its roots in Shannon s information theory and modem dynamical systems theory. This can explain why we had to wait the last decade before these dynamical aspects of the second law were discovered. 

Numerical simulations were performed in the authors group in order to better understand experimental observations [77, 80]. They are based on minimal assumptions about the system a random distribution of TLS s in space around the molecule, an interaction decreasing like the inverse cubic distance between molecule and TLS, and a broad spread of asymmetries and jumping times due to tunneling dynamics and disorder. No correlation was assumed between jumping rates, asymmetries and distances from the molecule. Simulated lineshapes and correlation functions ate qualitatively similar to experimental data (Fig. 13). They confirm that the isolation of a single TLS in the correlation function is possible, even when several... 

---