Thermodynamic constraints on fluctuation phenomena.

نویسنده

  • O J E Maroney
چکیده

The relationships among reversible Carnot cycles, the absence of perpetual motion machines, and the existence of a nondecreasing globally unique entropy function form the starting point of many textbook presentations of the foundations of thermodynamics. However, the thermal fluctuation phenomena associated with statistical mechanics has been argued to restrict the domain of validity of this basis of the second law of thermodynamics. Here we demonstrate that fluctuation phenomena can be incorporated into the traditional presentation, extending rather than restricting the domain of validity of the phenomenologically motivated second law. Consistency conditions lead to constraints upon the possible spectrum of thermal fluctuations. In a special case this uniquely selects the Gibbs canonical distribution and more generally incorporates the Tsallis distributions. No particular model of microscopic dynamics need be assumed.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Information in Biological Systems and the Fluctuation Theorem

Some critical trends in information theory, its role in living systems and utilization in fluctuation theory are discussed. The mutual information of thermodynamic coupling is incorporated into the generalized fluctuation theorem by using information theory and nonequilibrium thermodynamics. Thermodynamically coupled dissipative structures in living systems are capable of degrading more energy,...

متن کامل

Fluctuations When Driving Between Nonequilibrium Steady States

Maintained by environmental fluxes, biological systems are thermodynamic processes that operate far from equilibrium without detailed-balance dynamics. Yet, they often exhibit well defined nonequilibrium steady states (NESSs). More importantly, critical thermodynamic functionality arises directly from transitions among their NESSs, driven by environmental switching. Here, we identify constraint...

متن کامل

Valence fluctuation phenomena

Valence fluctuation phenomena occur in rare-earth compounds in which the proximity of the 4f level to the Fermi energy leads to instabilities of the charge configuration (valence) and/or of the magnetic moment. We review the experimental results observed in the subset of such systems for which the 4f ions form a lattice with identical valence on each site. The discussion includes key thermodyna...

متن کامل

Langevin dynamics with constraints and computation of free energy differences

In this paper, we consider Langevin processes with mechanical constraints. The latter are a fundamental tool in molecular dynamics simulation for sampling purposes and for the computation of free energy differences. The results of this paper can be divided into three parts. (i) We propose a simple discretization of the constrained Langevin process based on a standard splitting strategy. We show...

متن کامل

Thermodynamic Characterization of the Aggregation Phenomena of Safranine‌T by Spectral Titration and Chemometric Analysis

The dimerization constants of Safranine T have been determined by studying the dependence of its absorption spectra on the temperature in the range 30–70 ◦C at different total concentrations of Safranine T (1.03×10−5, 1.44×10−5 and 1.73×10−5 M). The monomer–dimer equilibrium of Safranine T has been determined by applying MCR-ALS method on the absorpti...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Physical review. E, Statistical, nonlinear, and soft matter physics

دوره 80 6 Pt 1  شماره 

صفحات  -

تاریخ انتشار 2009