Exact density functional for hard rod mixtures derived from Markov chain approach

TL;DR

This paper derives an exact density functional for one-dimensional hard rod mixtures using a Markov chain approach, providing a fundamental basis for lattice density functional theory.

Contribution

It introduces a Markov chain method to rederive the exact density functional for lattice hard rod mixtures, linking microstate distributions to density profiles.

Findings

Exact expression for equilibrium microstate distribution

Unique external potential for given density profile

Additive mixture property from rod end placement

Abstract

Using a Markov chain approach we rederive the exact density functional for hard rod mixtures on a one-dimensional lattice, which forms the basis of the lattice fundamental measure theory. The transition probability in the Markov chain depends on a set of occupation numbers, which reflects the property of a zero-dimensional cavity to hold at most one particle. For given mean occupation numbers (density profile), an exact expression for the equilibrium distribution of microstates is obtained, that means an expression for the unique external potential that generates the density profile in equilibrium. By considering the rod ends to fall onto lattice sites, the mixture is always additive.