Construction of the free energy landscape by the density functional theory

TL;DR

This paper defines the free energy landscape within density functional theory and demonstrates its application by analyzing atomic rearrangements in an FCC crystal of hard spheres, revealing new concepts like SRR and CRR.

Contribution

It introduces a clear definition of the free energy landscape in DFT and applies it to atomic rearrangements, establishing explicit methods to identify CRR and SRR.

Findings

CRR is related to spheres involved in saddle points.

SRR is defined by differences between adjacent basins.

Explicit determination of CRR and SRR from the landscape.

Abstract

On the basis of the density functional theory, we give a clear definition of the free energy landscape. To show the usefulness of the definition, we construct the free energy landscape for rearrangement of atoms in an FCC crystal of hard spheres. In this description, the cooperatively rearranging region (CRR) is clealy related to the hard spheres involved in the saddle between two adjacent basins. A new concept of the simultaneously rearranging region (SRR) emerges naturally as spheres defined by the difference between two adjacent basins. We show that the SRR and the CRR can be determined explicitly from the free energylandscape.