Fluctuation Theorem - The Fluctuation Theorem and Loschmidt's Paradox

The Fluctuation Theorem and Loschmidt's Paradox

The second law of thermodynamics, which predicts that the entropy of an isolated system out of equilibrium should tend to increase rather than decrease or stay constant, stands in apparent contradiction with the time-reversible equations of motion for classical and quantum systems. The time reversal symmetry of the equations of motion show that if one films a given time dependent physical process, then playing the movie of that process backwards does not violate the laws of mechanics. It is often argued that for every forward trajectory in which entropy increases, there exists a time reversed anti trajectory where entropy decreases, thus if one picks an initial state randomly from the system's phase space and evolves it forward according to the laws governing the system, decreasing entropy should be just as likely as increasing entropy. It might seem that this is incompatible with the second law of thermodynamics which predicts that entropy tends to increase. The problem of deriving irreversible thermodynamics from time-symmetric fundamental laws is referred to as Loschmidt's paradox.

The mathematical proof of the Fluctuation Theorem and in particular the Second Law Inequality shows that, given a non-equilibrium starting state, the probability of seeing its entropy increase is greater than the probability of seeing its entropy decrease - see The Fluctuation Theorem from Advances in Physics 51: 1529. However, as noted in section 6 of that paper, one could also use the same laws of mechanics to extrapolate backwards from a later state to an earlier state, and in this case the same reasoning used in the proof of the FT would lead us to predict the entropy was likely to have been greater at earlier times than at later times. This second prediction would be frequently violated in the real world, since it is often true that a given nonequilibrium system was at an even lower entropy in the past (although the prediction would be correct if the nonequilibrium state were the result of a random fluctuation in entropy in an isolated system that had previously been at equilibrium - in this case, if you happen to observe the system in a lower-entropy state, it is most likely that you are seeing the minimum of the random dip in entropy, in which case entropy would be higher on either side of this minimum).

So, it seems that the problem of deriving time-asymmetric thermodynamic laws from time-symmetric laws cannot be solved by appealing to statistical derivations which show entropy is likely to increase when you start from a nonequilibrium state and project it forwards. Many modern physicists believe the resolution to this puzzle lies in the low-entropy state of the universe shortly after the big bang, although the explanation for this initial low entropy is still debated.

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