Abstract
We introduce axiomatically a complete thermodynamic formalism for a single macromolecule, either with or without detailed balance, in an isothermal ambient fluid based on its stochastic dynamics. With detailed balance, the theory yields mesoscopic, nonequilibrium for entropy (Upsilon(t)) and free energy (Psi(t)) of the macromolecule. Upsilon(t) and Psi(t) fluctuate. Expectation (d/dt)E[Psi(t)]< or =0, "="holds if and only if the macromolecule is at thermal equilibrium, in which we show that Upsilon(t) still fluctuates but Psi(t) is a constant. The entropy fluctuation of Landau, E[(DeltaUpsilon(t))(2)], precisely matches the fluctuation in the internal energy, which in turn equals the fluctuation in heat dissipation. As a generalization of Clausius' classic result, the dynamic fluctuations in the entropy and energy of the macromolecule are exactly compensated at thermal equilibrium. For systems with detailed balance, Helmholtz free energy is shown to be the potential of Onsager's thermodynamic force.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.