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The gain of free energy upon unmixing is determined via application of Markov state modeling (MSM), using an Ising model with a fixed number of up- and down-spins. MSM yields reasonable estimates of the free energies. However, a closer look…

Computational Physics · Physics 2017-08-02 Myra Biedermann , Andreas Heuer

Considering the increasing size of available data, the need for statistical methods that control the finite sample bias is growing. This is mainly due to the frequent settings where the number of variables is large and allowed to increase…

Statistics Theory · Mathematics 2018-10-12 Stéphane Guerrier , Mucyo Karemera , Samuel Orso , Maria-Pia Victoria-Feser

Many enhanced sampling techniques rely on the identification of a number of collective variables that describe all the slow modes of the system. By constructing a bias potential in this reduced space one is then able to sample efficiently…

Computational Physics · Physics 2019-03-05 Michele Invernizzi , Michele Parrinello

Biased sampling in molecular dynamics simulations overcomes timescale limitations and delivers free-energy landscapes, essential to understand complex atomistic phenomena. However, when applied across diverse systems and processes, biasing…

Statistical Mechanics · Physics 2026-01-14 Eline K. Kempkes , Alberto Pérez de Alba Ortíz

Atomistic modelling of phase transitions, chemical reactions, or other rare events that involve overcoming high free energy barriers usually entails prohibitively long simulation times. Introducing a bias potential as a function of an…

Computational Physics · Physics 2019-11-06 Federico Giberti , Bingqing Cheng , Gareth Aneurin Tribello , Michele Ceriotti

An important challenge in statistical analysis concerns the control of the finite sample bias of estimators. For example, the maximum likelihood estimator has a bias that can result in a significant inferential loss. This problem is…

Statistics Theory · Mathematics 2019-11-04 Stéphane Guerrier , Mucyo Karemera , Samuel Orso , Maria-Pia Victoria-Feser

In state space models, smoothing refers to the task of estimating a latent stochastic process given noisy measurements related to the process. We propose an unbiased estimator of smoothing expectations. The lack-of-bias property has…

Methodology · Statistics 2018-09-07 Pierre E. Jacob , Fredrik Lindsten , Thomas B. Schön

The ability of widely used sampling methods, such as molecular dynamics or Monte Carlo, to explore complex free energy landscapes is severely hampered by the presence of kinetic bottlenecks. A large number of solutions have been proposed to…

Statistical Mechanics · Physics 2014-08-29 Omar Valsson , Michele Parrinello

This paper applies the Bayesian Model Averaging (BMA) statistical ensemble technique to estimate small molecule solvation free energies. There is a wide range of methods available for predicting solvation free energies, ranging from…

Biomolecules · Quantitative Biology 2016-12-16 Luke J. Gosink , Christopher C. Overall , Sarah M. Reehl , Paul D. Whitney , David L. Mobley , Nathan A. Baker

This report presents the application of polynomial regression for estimating free energy differences using thermodynamic integration. We employ linear regression to construct a polynomial that optimally fits the thermodynamic integration…

Computational Physics · Physics 2008-10-02 Conrad Shyu , F. Marty Ytreberg

Entropy and free-energy estimation are key in thermodynamic characterization of simulated systems ranging from spin models through polymers, colloids, protein structure, and drug-design. Current techniques suffer from being model specific,…

Statistical Mechanics · Physics 2019-10-30 Ram Avinery , Micha Kornreich , Roy Beck

We develop a novel data-driven approach to the inverse problem of classical statistical mechanics: given experimental data on the collective motion of a classical many-body system, how does one characterise the free energy landscape of that…

Statistical Mechanics · Physics 2022-03-01 Peter Yatsyshin , Serafim Kalliadasis , Andrew B. Duncan

We explore how violations of the often-overlooked standard assumption that the random effects model matrix in a linear mixed model is fixed (and thus independent of the random effects vector) can lead to bias in estimators of estimable…

Statistics Theory · Mathematics 2020-06-23 Andrew T. Karl , Dale L. Zimmerman

The free energy functional has recently been proposed as a variational principle for bounded rational decision-making, since it instantiates a natural trade-off between utility gains and information processing costs that can be…

Machine Learning · Statistics 2012-05-18 Pedro A. Ortega , Daniel A. Braun

The estimation of rare event probabilities plays a pivotal role in diverse fields. Our aim is to determine the probability of a hazard or system failure occurring when a quantity of interest exceeds a critical value. In our approach, the…

Methodology · Statistics 2025-04-11 Lea Friedli , David Ginsbourger , Arnaud Doucet , Niklas Linde

In all applications in digital communications, it is crucial for an estimator to be unbiased. Although so-called soft feedback is widely employed in many different fields of engineering, typically the biased estimate is used. In this paper,…

Information Theory · Computer Science 2018-02-21 Susanne Sparrer , Robert F. H. Fischer

The estimation of risk measures recently gained a lot of attention, partly because of the backtesting issues of expected shortfall related to elicitability. In this work we shed a new and fundamental light on optimal estimation procedures…

Risk Management · Quantitative Finance 2017-08-25 Marcin Pitera , Thorsten Schmidt

Most methods for estimating configurational entropy from molecular simulation data yield upper limits except for harmonic systems where they are exact. Problems arise at diffusive systems and the presence of conformational transitions.…

Chemical Physics · Physics 2019-10-22 Jürgen Schlitter , Matthias Massarczyk

We introduce a classical estimator for the post-processing of quantum phase estimation data generated either by quantum-Fourier-transform-based or quantum-signal-processing-based methods. We focus on the estimation of a single target phase…

Quantum Physics · Physics 2026-03-24 Alicja Dutkiewicz , Thomas E. O'Brien , Stefano Polla

We derive the optimal estimates of the free energies of an arbitrary number of thermodynamic states from nonequilibrium work measurements; the work data are collected from forward and reverse switching processes and obey a fluctuation…

Statistical Mechanics · Physics 2009-11-11 Paul Maragakis , Martin Spichty , Martin Karplus