The Quantum Method of Planes - Local Pressure Definitions for Machine Learning Potentials

Abstract: Stress or Pressure is a central quantity in engineering, and remains vital in molecular modelling. However, the commonly used virial stress tensor is not valid away from thermodynamic equilibrium, a common state required in fluid dynamics and non-equilibrium molecular dynamics (NEMD) simulation. This is solved by using the method of planes (MoP), a mechanical form of pressure, simply interpreted as the force divided by area but derived from the firm foundations of statistical mechanics. We present an extension of MoP stress to the MACE potential, a particular form of ML potentials allowing quantum mechanical (QM) physics in classical simulation. We present the derivation of the MoP stress for the MACE potential using the theoretical framework set out by Irving & Kirkwood (1950). For the testcase of an interface between water and Zirconium Oxide, we show the MoP measures the correct force balance while the virial form fails. Further, we demonstrate the MoP is valid arbitrarily far from equilibrium, showing exact conservation every timestep in a control volume bounded by MoP planes. This links the stress directly to the conservation equations and demonstrates the validity in non equilibrium molecular dynamics systems. All code to reproduce these validations for any MACE system, together with ASE accelerated code to calculate the MoP are provided as open source. This work helps build the foundation to extend the ML revolution in materials to NEMD and molecular fluid dynamics modelling.