Calculation of local pressure tensors in systems with many-body interactions

TL;DR

This paper introduces a method to calculate local pressures in systems with many-body interactions, extending previous pairwise approaches, and demonstrates its effectiveness through numerical examples like liquid propane.

Contribution

A novel approach for computing local pressures in systems with n-body interactions, compatible with existing hydrodynamic formulas and applicable to complex materials.

Findings

Method accurately computes local pressures with many-body interactions.

Numerical example confirms equivalence with existing approaches.

Allows analysis of local pressures in complex atomistic simulations.

Abstract

Local pressures are important in the calculation of interface tensions and in analyzing micromechanical behavior. The calculation of local pressures in computer simulations has been limited to systems with pairwise interactions between the particles, which is not sufficient for chemically detailed systems with many-body potentials such as angles and torsions. We introduce a method to calculate local pressures in systems with n-body interactions (n=2,3,4, . . .) based on a micromechanical definition of the pressure tensor. The local pressure consists of a kinetic contribution from the linear momentum of the particles and an internal contribution from dissected many-body interactions by infinitesimal areas. To define dissection by a small area, respective n-body interactions are divided into two geometric centers, effectively reducing them to two-body interactions. Consistency with hydrodynamics-derived formulas for systems with two-body interactions (J. H. Irving and J. G. Kirkwood, J. Chem. Phys. 18, 817 (1950)), for average cross-sectional pressures (B. D. Todd, D. J. Evans, and P. J. Daivis, Phys. Rev. E 52, 1627 (1995)), and for volume averaged pressures (virial formula) is shown. As a simple numerical example, we discuss liquid propane in a cubic box. Local, crosssectional,and volume-averaged pressures as well as relative contributions from two-body and three-body forces are analyzed with the proposed method, showing full numerical equivalence with the existing approaches. The method allows computing local pressures in the presence of many-body interactions in atomistic simulations of complex materials and biological systems.