Proper normalization removes nonlocal behavior of canonical-based thermodynamic entropy expressions
Source abstract
Abstract
Equilibrium, canonical based expressions of entropy are known to exhibit non-local effects that can complicate statistical mechanical formulations and applications. Here, we demonstrate that proper normalization of the underlying probability density functions can remove non-local effects in entropy. Our analysis is carried out through third order in density function expansions and lead to results consistent with macroscopic thermodynamics, as required. In addition, we provide complete expressions for smaller dimensional systems that may not conform to the thermodynamic limit.
Source: crossref · Quality: baseline
Research context
OpenAlex topics: Advanced Thermodynamics and Statistical Mechanics · Statistical Mechanics and Entropy · Spectroscopy and Quantum Chemical Studies
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Department of Chemical and Life Science Engineering, Virginia Commonwealth University , 601 West Main St., Richmond, Virginia 23284, USA
References (11)
Show source-provided references
1. 1952
2. Expressions in terms of molecular distribution functions for the entropy density in an infinite system10.1063/1.1744724 ↗
3. On the role of density fluctuations in the entropy of a fluid10.1063/1.453158 ↗
4. Entropy and molecular correlation functions in open systems. I. Derivation10.1063/1.1676399 ↗
5. Direct entropy calculation from computer simulation of liquids10.1103/physreva.40.3817 ↗
6. Maximum entropy formulations of the Kirkwood superposition approximation10.1063/1.1776552 ↗
7. The Sackur-Tetrode equation: How entropy met quantum mechanics
8. J. Chem. Phys. · 1942 · 10 · 39410.1063/1.1723737 ↗
9. 1976
10. 1969
11. 1977