Lee-Yang Theory Guided Force Field Refinement Based on Phase Diagrams

Abstract

We propose a general framework for automatic force field refinement guided by phase diagrams, grounded in Lee-Yang phase transition theory. The central idea is to directly use the partition function modulus as a phase-diagram-guided optimization target. Evaluating the modulus at points close to the real axis, where the Lee-Yang zeros are mostly associated with the phase transition, is more physically meaningful and avoids the numerical difficulty of explicitly solving for the zeros. This approach requires no system-specific order parameters or response properties for characterizing phase transition points, making it universal across various discontinuous phase transitions and material systems. We validate the method on refining parameters of a Lennard-Jones potential covering both gas-liquid and solid-liquid transitions, and a Cu embedded-atom method potential based on experimental melting curves. The refined force fields reproduce the target phase diagrams with significant improvement across all systems. For Cu, the refinement simultaneously improves predictions of enthalpy and heat capacity, which are observables beyond the optimization target. These results establish Lee-Yang theory as a practical tool for contemporary force field development.