TY - JOUR

T1 - On the relationship between dissipation and the rate of spontaneous entropy production from linear irreversible thermodynamics

AU - Williams, Stephen R.

AU - Searles, Debra J.

AU - Evans, Denis J.

PY - 2014

Y1 - 2014

N2 - When systems are far from equilibrium, the temperature, the entropy and the thermodynamic entropy production are not defined and the Gibbs entropy does not provide useful information about the physical properties of a system. Furthermore, far from equilibrium, or if the dissipative field changes in time, the spontaneous entropy production of linear irreversible thermodynamics becomes irrelevant. In 2000 we introduced a definition for the dissipation function and showed that for systems of arbitrary size, arbitrarily near or far from equilibrium, the time integral of the ensemble average of this quantity can never decrease. In the low-field limit, its ensemble average becomes equal to the spontaneous entropy production of linear irreversible thermodynamics. We discuss how these quantities are related and why one should use dissipation rather than entropy or entropy production for non-equilibrium systems.

AB - When systems are far from equilibrium, the temperature, the entropy and the thermodynamic entropy production are not defined and the Gibbs entropy does not provide useful information about the physical properties of a system. Furthermore, far from equilibrium, or if the dissipative field changes in time, the spontaneous entropy production of linear irreversible thermodynamics becomes irrelevant. In 2000 we introduced a definition for the dissipation function and showed that for systems of arbitrary size, arbitrarily near or far from equilibrium, the time integral of the ensemble average of this quantity can never decrease. In the low-field limit, its ensemble average becomes equal to the spontaneous entropy production of linear irreversible thermodynamics. We discuss how these quantities are related and why one should use dissipation rather than entropy or entropy production for non-equilibrium systems.

KW - dissipation

KW - fluctuation theorem

KW - linear irreversible thermodynamics

KW - non-equilibrium

KW - statistical mechanics

UR - http://www.scopus.com/inward/record.url?scp=84896744284&partnerID=8YFLogxK

U2 - 10.1080/08927022.2013.843175

DO - 10.1080/08927022.2013.843175

M3 - Article

SN - 0892-7022

VL - 40

SP - 208

EP - 217

JO - Molecular Simulation

JF - Molecular Simulation

IS - 1-3

ER -