Enhancing Important Fluctuations: Rare Events and Metadynamics from a Conceptual Viewpoint

2016/03/16 by Ómar Valsson, Omar Valsson, Pratyush Tiwary +1 · 698 citations
Chemistry · Earth and Planetary Sciences · Mathematics · Physics and Astronomy · #Advanced Thermodynamics and Statistical Mechanics #Artificial intelligence #Chemistry #Complex system #Computational chemistry #Computer science #Mathematics #Metadynamics #Metastability #Molecular dynamics #Physics #Quantum mechanics #Rare events #Sampling (signal processing) #Statistical physics #Statistics #Theoretical and Computational Physics #Variety (cybernetics) #nanoparticles nucleation surface interactions

paper · pdf · doi:10.1146/annurev-physchem-040215-112229

published in Annual Review of Physical Chemistry 67(1), 159-184 (Annual Reviews)

openalex publication_date 2016/03/16 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/31

Abstract

Atomistic simulations play a central role in many fields of science. However, their usefulness is often limited by the fact that many systems are characterized by several metastable states separated by high barriers, leading to kinetic bottlenecks. Transitions between metastable states are thus rare events that occur on significantly longer timescales than one can simulate in practice. Numerous enhanced sampling methods have been introduced to alleviate this timescale problem, including methods based on identifying a few crucial order parameters or collective variables and enhancing the sampling of these variables. Metadynamics is one such method that has proven successful in a great variety of fields. Here we review the conceptual and theoretical foundations of metadynamics. As demonstrated, metadynamics is not just a practical tool but can also be considered an important development in the theory of statistical mechanics.

Citations

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