Bidirectional-Stability Breaking in Thermodynamic Average for Classical Discrete Systems

TL;DR

This paper investigates the stability of inverse determination of potential energy surfaces in classical discrete systems, revealing that stability breaking is governed by geometric properties of the lattice, independent of thermodynamic variables.

Contribution

It quantitatively formulates how bidirectional stability breaks in thermodynamic averages, linking it to geometric lattice information without thermodynamic data.

Findings

Stability breaking is dominated by divergence and Jacobian of a vector field in configuration space.

The stability breaking can be predicted solely from lattice geometry.

A new quantitative framework for stability analysis in classical systems is proposed.

Abstract

For classical systems, expectation value of macroscopic property in equilibrium state can be typically provided through thermodynamic (so-called canonical) average, where summation is taken over possible states in phase space (or in crystalline solids, it is typically approximated on cofiguration space). Although we have a number of theoretical approaches enabling to quantitatively estimate equilibrium properties by applying given potential energy surface (PES) to the thermodynamic average, it is generally unclear whether PES can be stablly, inversely determined from a given set of properties. This essentially comes from the fact that bidirectional stability characters of thermodynamic average for classical system is not sufficiently understood so far. Our recent study reveals that for classical discrete system, this property for a set of microscopic states satisfying special condition can be well-characterized by a newly-introduced concept of anharmonicity in the structural degree of freedom of D, where these states are expected to be stably inversed to underlying PES, known without any thermodynamic information. However, it is still quantitatively unclear how the bidirectional stability character is broken inside the configuration space. Here we show that the breaking in bidirectional stability for thermodynamic average is quantitatively formulated: We find that the breaking is mainly dominated by the sum of divergence and Jacobian of vector field D in configuration space, which can be fully known a priori only from geometric information of underlying lattice, without using any thermodynamic information such as energy or temperature.