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We present a new estimator for computing free energy differences and thermodynamic expectations as well as their uncertainties from samples obtained from multiple equilibrium states via either simulation or experiment. The estimator, which…

计算物理 · 物理学 2011-12-06 Michael R. Shirts , John D. Chodera

The multistate Bennett acceptance ratio (MBAR) method is a prevalent approach for computing free energies of thermodynamic states. In this work, we introduce BayesMBAR, a Bayesian generalization of the MBAR method. By integrating…

化学物理 · 物理学 2024-02-16 Xinqiang Ding

Free energy calculations based on atomistic Hamiltonians provide microscopic insight into the thermodynamic driving forces of biophysical or condensed matter systems. Many approaches use intermediate Hamiltonians interpolating between the…

计算物理 · 物理学 2021-12-08 Martin Reinhardt , Helmut Grubmüller

Umbrella sampling efficiently yields equilibrium averages that depend on exploring rare states of a model by biasing simulations to windows of coordinate values and then combining the resulting data with physical weighting. Here, we…

统计力学 · 物理学 2016-09-21 Erik Thiede , Brian Van Koten , Jonathan Weare , Aaron R. Dinner

The multistate Bennett Acceptance Ratio is provably the lowest variance unbiased estimator of both free energies and ensemble averages, and has a number of important advantages over previous methods, such as WHAM. Despite its advantages,…

统计力学 · 物理学 2017-12-20 Michael R. Shirts

Free energy difference calculations based on atomistic simulations generally improve in accuracy when sampling from a sequence of intermediate equilibrium thermodynamic states that bridge the configuration space between two states of…

计算物理 · 物理学 2020-10-21 Martin Reinhardt , Helmut Grubmüller

We show how thermodynamic properties of molecular models can be computed over a large, multidimensional parameter space by combining multistate reweighting analysis with a linear basis function approach. This approach reduces the…

化学物理 · 物理学 2016-05-18 Levi N. Naden , Michael R. Shirts

Free energy calculations based on atomistic Hamiltonians and sampling are key to a first principles understanding of biomolecular processes, material properties, and macromolecular chemistry. Here, we generalize the Free Energy Perturbation…

计算物理 · 物理学 2023-07-19 Martin Reinhardt , Helmut Grubmüller

Markov state models (MSMs) are widely employed to analyze the kinetics of complex systems. But despite their effectiveness in many applications, MSMs are prone to systematic or statistical errors, often exacerbated by suboptimal…

数据分析、统计与概率 · 物理学 2025-08-12 Yehor Tuchkov , Luke Evans , Sonya M. Hanson , Erik H. Thiede

Free energies are fundamental quantities governing phase behavior and thermodynamic stability in polymer systems, yet their accurate computation often requires extensive simulations and post-processing techniques such as the Bennett…

软凝聚态物质 · 物理学 2026-03-19 Ian Chen , Alfredo Alexander-Katz

Umbrella sampling is an efficient method for the calculation of free energy changes of a system along well-defined reaction coordinates. However, when multiple parallel channels along the reaction coordinate or hidden barriers in directions…

统计方法学 · 统计学 2015-06-16 Mingjun Yang , Lijiang Yang , Yiqin Gao , Hao Hu

The dynamics of molecules are governed by rare event transitions between long-lived (metastable) states. To explore these transitions efficiently, many enhanced sampling protocols have been introduced that involve using simulations with…

化学物理 · 物理学 2022-09-30 Maaike M. Galama , Hao Wu , Andreas Krämer , Mohsen Sadeghi , Frank Noé

In Markov Chain Monte Carlo (MCMC) simulations, the thermal equilibria quantities are estimated by ensemble average over a sample set containing a large number of correlated samples. These samples are selected in accordance with the…

数据分析、统计与概率 · 物理学 2015-01-08 J. Li , P. Vignal , S. Sun , V. M. Calo

Free energy profile (FE Profile) is an essential quantity for the estimation of reaction rate and the validation of reaction mechanism. For chemical reactions in condensed phase or enzymatic reactions, the computation of FE profile at ab…

计算物理 · 物理学 2018-11-15 Pengfei Li , Xiangyu Jia , Xiaoliang Pan , Yihan Shao , Ye Mei

Free energy of crystal phases is commonly evaluated by thermodynamic integration (TDI) along a reversible path that involves an external potential. A persistent problem in this method is that a significant hysteresis is observed due to…

材料科学 · 物理学 2010-02-27 Pankaj A. Apte

An efficient sampling method, the pmmLang+RBM, is proposed to compute the quantum thermal average in the interacting quantum particle system. Benefiting from the random batch method (RBM), the pmmLang+RBM reduces the complexity due to the…

量子物理 · 物理学 2021-06-16 Xuda Ye , Zhennan Zhou

Computing the equilibrium properties of complex systems, such as free energy differences, is often hampered by rare events in the dynamics. Enhanced sampling methods may be used in order to speed up sampling by, for example, using high…

计算物理 · 物理学 2015-02-11 Antonia S. J. S. Mey , Hao Wu , Frank Noé

In QM/MM indirect free energy simulation, QM/MM corrections can be obtained from integration of partial derivatives of alchemical Hamiltonians or from perturbation-based estimators including free energy perturbation (FEP) and acceptance…

化学物理 · 物理学 2018-10-05 Xiaohui Wang , Zhaoxi Sun

The conformational free energy landscape of a system is a fundamental thermodynamic quantity of importance particularly in the study of soft matter and biological systems, in which the entropic contributions play a dominant role. While…

生物物理 · 物理学 2015-10-13 N. Ramakrishnan , Richard W. Tourdot , Ravi Radhakrishnan

The naive importance sampling estimator, based on samples from a single importance density, can be numerically unstable. Instead, we consider generalized importance sampling estimators where samples from more than one probability…

统计理论 · 数学 2016-08-12 Vivekananda Roy , Aixin Tan , James M. Flegal
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