Adrianne Zhong, Ben Kuznets-Speck, Michael R. DeWeese
{"title":"Time-asymmetric fluctuation theorem and efficient free-energy estimation","authors":"Adrianne Zhong, Ben Kuznets-Speck, Michael R. DeWeese","doi":"10.1103/physreve.110.034121","DOIUrl":null,"url":null,"abstract":"The free-energy difference <math xmlns=\"http://www.w3.org/1998/Math/MathML\"><mrow><mi mathvariant=\"normal\">Δ</mi><mi>F</mi></mrow></math> between two high-dimensional systems is notoriously difficult to compute but very important for many applications such as drug discovery. We demonstrate that an unconventional definition of work introduced by Vaikuntanathan and Jarzynski (2008) satisfies a microscopic fluctuation theorem that relates path ensembles that are driven by protocols unequal under time reversal. It has been shown before that counterdiabatic protocols—those having additional forcing that enforces the system to remain in instantaneous equilibrium, also known as escorted dynamics or engineered swift equilibration—yield zero-variance work measurements for this definition. We show that this time-asymmetric microscopic fluctuation theorem can be exploited for efficient free-energy estimation by developing a simple (i.e., neural-network free) and efficient adaptive time-asymmetric protocol optimization algorithm that yields <math xmlns=\"http://www.w3.org/1998/Math/MathML\"><mrow><mi mathvariant=\"normal\">Δ</mi><mi>F</mi></mrow></math> estimates that are orders of magnitude lower in mean squared error than the generic linear interpolation protocol with which it is initialized.","PeriodicalId":20085,"journal":{"name":"Physical review. E","volume":null,"pages":null},"PeriodicalIF":2.4000,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical review. E","FirstCategoryId":"101","ListUrlMain":"https://doi.org/10.1103/physreve.110.034121","RegionNum":3,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"Mathematics","Score":null,"Total":0}
引用次数: 0
Abstract
The free-energy difference between two high-dimensional systems is notoriously difficult to compute but very important for many applications such as drug discovery. We demonstrate that an unconventional definition of work introduced by Vaikuntanathan and Jarzynski (2008) satisfies a microscopic fluctuation theorem that relates path ensembles that are driven by protocols unequal under time reversal. It has been shown before that counterdiabatic protocols—those having additional forcing that enforces the system to remain in instantaneous equilibrium, also known as escorted dynamics or engineered swift equilibration—yield zero-variance work measurements for this definition. We show that this time-asymmetric microscopic fluctuation theorem can be exploited for efficient free-energy estimation by developing a simple (i.e., neural-network free) and efficient adaptive time-asymmetric protocol optimization algorithm that yields estimates that are orders of magnitude lower in mean squared error than the generic linear interpolation protocol with which it is initialized.
期刊介绍:
Physical Review E (PRE), broad and interdisciplinary in scope, focuses on collective phenomena of many-body systems, with statistical physics and nonlinear dynamics as the central themes of the journal. Physical Review E publishes recent developments in biological and soft matter physics including granular materials, colloids, complex fluids, liquid crystals, and polymers. The journal covers fluid dynamics and plasma physics and includes sections on computational and interdisciplinary physics, for example, complex networks.