Maximum entropy methods as the bridge between microscopic and macroscopic theory

Journal article

This paper is concerned with an investigation into a function of macroscopic variables known as the singular potential, building on previous work by Ball and Majumdar. The singular potential is a function of the admissible statistical averages of probability distributions on a state space, defined so that it corresponds to the maximum possible entropy given known observed statistical averages, although non-classical entropy-like objective functions will also be considered. First the set of admissible moments must be established, and under the conditions presented in this work the set is open, bounded and convex allowing a description in terms of supporting hyperplanes, which provides estimates on the development of singularities for related probability distributions. Under appropriate conditions it is shown that the singular potential is strictly convex, as differentiable as the microscopic entropy, and blows up uniformly as the macroscopic variable tends to the boundary of the set of admissible moments. Applications of the singular potential are then discussed, and particular consideration will be given to certain free-energy functionals typical in mean-field theory, demonstrating an equivalence between certain microscopic and macroscopic free-energy functionals. This allows statements about L1-local minimisers of Onsager’s free energy to be obtained which cannot be given by two-sided variations, and overcomes the need to ensure local minimisers are bounded away from zero and + ∞ before taking L∞ variations. The analysis also permits the definition of a dual order parameter for which Onsager’s free energy allows an explicit representation. Also, the difficulties in approximating the singular potential by everywhere defined functions, in particular by polynomial functions, are addressed, with examples demonstrating the failure of the Taylor approximation to preserve relevant shape properties of the singular potential.

Authors: Taylor, J

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: Springer US
• Journal: Journal of Statistical Physics
• Volume: 164
• Issue: 6
• Pages: 1429-1459
• Publication date: 2016-09-01
• Acceptance date: 2016-07-12
• DOI: 10.1007/s10955-016-1587-8
• EISSN: 1572-9613
• ISSN: 0022-4715
• Keywords: liquid crystals; order parameter constraints; maximum entropy methods; mean-field theory