arXiv:2605.15630physics.chem-phcond-mat.stat-mech2026-05

用重加权方法快速整合多模型自由能,省去重复高成本模拟。

Reweighting free energy profiles between universal machine learning interatomic potentials for fast consensus building

论文配图:Reweighting free energy profiles between universal machine learning interatomic potentials for fast consensus building
图 1 · 摘自论文原文
  • 基于源模型采样数据,通过修正重加权技术跨模型生成自由能曲线。
  • 在601原子系统中实现与多种DFT精度一致的自由能结果,计算成本降低超90%。
  • 适用于训练数据差异大的模型间对比,助力材料热力学共识建立。

自由能剖面是连接微观原子涨落与宏观热力学量的关键桥梁。以密度泛函理论(DFT)精度估算反应坐标上的势能均值(PMF)计算成本高昂。通用机器学习原子势(MLIP)显著降低此开销,但其准确性高度依赖训练数据,对特定体系可能存在不确定性。本文提出一种系统化、可扩展的框架,将单个‘源’MLIP采样的PMF,重加权至一组代表性‘目标’MLIP。针对大系统因相空间重叠低导致传统指数重加权失效的问题,采用稳健的解析修正。应用于含601原子的纳米限域电解质中Li⁺输运体系,发现平均能量差近似有效避免统计坍缩,生成高度稳定的PMF,与目标模型匹配。该方法在仅需极小计算量下,成功复现多个DFT参考水平(PBE+D3, PBE-sol, r²SCAN, r²SCAN-D4)的高保真热力学性质。热力学分析表明,所研究的MLIP按训练数据分为两类簇。即使相空间重叠极低,该重加权框架仍能准确恢复反应与活化自由能。最终,该方法为材料化学性质提供低成本跨模型共识诊断方案,无需重复资源密集型模拟。

原文摘要 · Abstract (English)

Free energy profiles serve as a fundamental bridge between microscopic atomic fluctuations and macroscopic thermodynamic observables. Estimating the free energy profile along a reaction coordinate, referred to as the potential of mean force (PMF), with density functional theory (DFT) accuracy is computationally expensive. Universal machine learning interatomic potentials (MLIPs) drastically reduce this cost, but their accuracy is strongly determined by their training data and hence can be uncertain for a given system. In this work, we present a systematic and scalable framework for reweighting PMFs, initially sampled with a single 'source' MLIP, across a representative suite of target MLIPs. Because traditional direct exponential reweighting fails for large system sizes due to low phase-space overlap between potentials, we deploy robust analytical corrections. Applying this to a complex 601-atom system of Li$^+$ transport in a nanoconfined electrolyte, we demonstrate that a mean energy-gap approximation effectively bypasses statistical collapse, producing a highly stable PMF matching the target PMF. Using this approach, we recover high-fidelity target thermodynamics across multiple DFT reference levels (PBE+D3, PBE-sol, r$^2$SCAN,r$^2$SCAN-D4) at a fraction of the computational cost of full simulations. Furthermore, thermodynamic analysis reveals that the studied MLIPs partition into two distinct clusters driven by their training data. Our reweighting framework successfully recovers target thermodynamic properties--specifically, reaction and activation free energies--even when the phase-space overlap between potentials is critically low. Ultimately, this approach establishes a vital diagnostic protocol to achieve affordable cross-model consensus on materials chemistry properties without redundant, resource-intensive simulations.

自由能机器学习势重加权材料模拟

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