Thermodynamics of Markov Processes with Non-extensive Entropy and Free Energy


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Statistical thermodynamics of small systems shows dramatic differences from normal systems. Parallel to the recently presented steady-state thermodynamic formalism for master equation and Fokker-Planck equation, we show that a ``thermodynamic theory can also be developed based on Tsallis generalized entropy $S^{(q)}=sum_{i=1}^N(p_i-p_i^q)/[q(q-1)]$ and Shiinos generalized free energy $F^{(q)}=[sum_{i=1}^Np_i(p_i/pi_i)^{q-1}-1]/[q(q-1)]$, where $pi_i$ is the stationary distribution. $dF^{(q)}/dt=-f_d^{(q)}le 0$ and it is zero iff the system is in its stationary state. $dS^{(q)}/dt-Q_{ex}^{(q)} = f_d^{(q)}$ where $Q_{ex}^{(q)}$ characterizes the heat exchange. For systems approaching equilibrium with detailed balance, $f_d^{(q)}$ is the product of Onsagers thermodynamic flux and force. However, it is discovered that the Onsagers force is non-local. This is a consequence of the particular transformation invariance for zero energy of Tsallis statistics.

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