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Precise determination of pair interactions from pair statistics of many-body systems in and out of equilibrium

Salvatore Torquato1,2,* and Haina Wang3

  • 1Department of Chemistry, Department of Physics, Princeton Institute of Materials, and Program in Applied and Computational Mathematics, Princeton University, Princeton, New Jersey 08544, USA
  • 2School of Natural Sciences, Institute for Advanced Study, 1 Einstein Drive, Princeton, New Jersey 08540, USA
  • 3Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA

  • *torquato@princeton.edu
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Phys. Rev. E 106, 044122 – Published 14 October, 2022

DOI: https://doi.org/10.1103/PhysRevE.106.044122

Abstract

The determination of the pair potential v(r) that accurately yields an equilibrium state at positive temperature T with a prescribed pair correlation function g2(r) or corresponding structure factor S(k) in d-dimensional Euclidean space Rd is an outstanding inverse statistical mechanics problem with far-reaching implications. Recently, Zhang and Torquato [Phys. Rev. E 101, 032124 (2020)] conjectured that any realizable g2(r) or S(k) corresponding to a translationally invariant nonequilibrium system can be attained by a classical equilibrium ensemble involving only (up to) effective pair interactions. Testing this conjecture for nonequilibrium systems as well as for nontrivial equilibrium states requires improved inverse methodologies. We have devised an optimization algorithm to precisely determine effective pair potentials that correspond to pair statistics of general translationally invariant disordered many-body equilibrium or nonequilibrium systems at positive temperatures. This methodology utilizes a parameterized family of pointwise basis functions for the potential function whose initial form is informed by small-, intermediate- and large-distance behaviors dictated by statistical-mechanical theory. Subsequently, a nonlinear optimization technique is utilized to minimize an objective function that incorporates both the target pair correlation function g2(r) and structure factor S(k) so that the small intermediate- and large-distance correlations are very accurately captured. To illustrate the versatility and power of our methodology, we accurately determine the effective pair interactions of the following four diverse target systems: (1) Lennard-Jones system in the vicinity of its critical point, (2) liquid under the Dzugutov potential, (3) nonequilibrium random sequential addition packing, and (4) a nonequilibrium hyperuniform “cloaked” uniformly randomized lattice. We found that the optimized pair potentials generate corresponding pair statistics that accurately match their corresponding targets with total L2-norm errors that are an order of magnitude smaller than that of previous methods. The results of our investigation lend further support to the Zhang-Torquato conjecture. Furthermore, our algorithm will enable one to probe systems with identical pair statistics but different higher-body statistics, which will shed light on the well-known degeneracy problem of statistical mechanics.

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Phys. Rev. E 106, 044122– Published 14 October, 2022
  • Received 23 May 2022
  • Revised 1 August 2022
  • Accepted 22 September 2022
Article part of CHORUS
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