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The potential of mean-field decomposition techniques in interpreting electronic transitions in molecules is explored, particularly, the usefulness of these for offering computational signatures of different classes of such excitations. When…

Chemical Physics · Physics 2022-02-14 Janus J. Eriksen

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

An analysis of the network defined by the potential energy minima of multi-atomic systems and their connectivity via reaction pathways that go through transition states allows to understand important characteristics like thermodynamic,…

Materials Science · Physics 2016-08-03 Bastian Schaefer , Stefan Goedecker

We study the effect of changes in the parameters of a two-dimensional potential energy surface on the phase space structures relevant for chemical reaction dynamics. The changes in the potential energy are representative of chemical…

Dynamical Systems · Mathematics 2021-07-28 Wenyang Lyu , Shibabrat Naik , Stephen Wiggins

We introduce an extension of a recently published method\cite{Mendels2018} to obtain low-dimensional collective variables for studying multiple states free energy processes in chemical reactions. The only information needed is a collection…

Computational Physics · Physics 2018-09-10 GiovanniMaria Piccini , Dan Mendels , Michele Parrinello

This article describes nonequilibrium techniques for the calculation of free energies of solids using molecular dynamics (MD) simulations. These methods provide an alternative to standard equilibrium thermodynamic integration methods and…

Materials Science · Physics 2022-01-13 Rodrigo Freitas , Mark Asta , Maurice de Koning

For classical discrete systems under constant composition typically refferred to substitutional alloys, we propose calculation method of Helmholtz free energy based on a set of special microscopic states. The advantage of the method is that…

Statistical Mechanics · Physics 2021-10-22 Ryogo Miyake , Subaru Sugie , Koretaka Yuge

We extend the non-parametric framework of reaction coordinate optimization to non-equilibrium ensembles of (short) trajectories. For example, we show how, starting from such an ensemble, one can obtain an equilibrium free energy profile…

Chemical Physics · Physics 2021-02-09 Sergei V. Krivov

Sampling from discrete distributions with multiple modes and energy barriers is fundamental to machine learning and computational physics. Recent discrete neural samplers like MDNS suffer from mode collapse and fail to sample high-energy…

Biased sampling methods such as the Temperature Accelerated Sliced Sampling (TASS), which can explore high dimensional collective variable (CV) space, is of great interest in free energy calculations. Such methods can efficiently sample…

Computational Physics · Physics 2020-10-06 Abhinav Gupta , Shivani Verma , Nisanth N. Nair

A simple, efficient, and accurate method is proposed to map multi-dimensional free energy landscapes. The method combines the temperature-accelerated molecular dynamics (TAMD) proposed in [Maragliano & Vanden-Eijnden, Chem. Phys. Lett. 426,…

Computational Physics · Physics 2009-11-13 Luca Maragliano , Eric Vanden-Eijnden

Metadynamics is a powerful computational tool to obtain the free energy landscape of complex systems. The Monte Carlo algorithm has proven useful to calculate thermodynamic quantities associated with simplified models of proteins, and thus…

Statistical Mechanics · Physics 2007-10-04 F. Marini , C. Camilloni , D. Provasi , R. A. Broglia , G. Tiana

The present paper proposes an adaptive biasing potential for the computation of free energy landscapes. It is motivated by statistical learning arguments and unifies the tasks of biasing the molecular dynamics to escape free energy wells…

Mathematical Physics · Physics 2018-03-05 I. Bilionis , P. S. Koutsourelakis

We propose a free-energy-perturbation approach accelerated by machine-learning potentials to efficiently compute transition temperatures and entropies for all rungs of Jacob's ladder. We apply the approach to the dynamically stabilized…

Materials Science · Physics 2025-05-05 Axel Forslund , Jong Hyun Jung , Yuji Ikeda , Blazej Grabowski

We present a method for determining the free energy dependence on a selected number of collective variables using an adaptive bias. The formalism provides a unified description which has metadynamics and canonical sampling as limiting…

Statistical Mechanics · Physics 2008-03-31 Alessandro Barducci , Giovanni Bussi , Michele Parrinello

Describing the complex landscape of infinite-dimensional free energy is generally a challenging problem. This difficulty arises from the existence of numerous minimizers and, consequently, a vast number of saddle points. These factors make…

Soft Condensed Matter · Physics 2025-07-15 Keiichiro Kagawa , Takeshi Watanabe , Yasumasa Nishiura

To expand the existing QUEST database of accurate vertical transition energies [\href{https://doi.org/10.1002/wcms.1517}{V\'eril et al.~\textit{WIREs Comput.~Mol.~Sci.} \textbf{2021}, \textit{11}, e1517}], we have modeled more than 100…

Chemical Physics · Physics 2024-01-26 Pierre-François Loos , Denis Jacquemin

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…

Computational Physics · Physics 2023-07-19 Martin Reinhardt , Helmut Grubmüller

The computational study of conformational transitions in RNA and proteins with atomistic molecular dynamics often requires suitable enhanced sampling techniques. We here introduce a novel method where concurrent metadynamics are integrated…

Computational Physics · Physics 2015-09-01 Alejandro Gil-Ley , Giovanni Bussi

Describing chemical reactions in solution on a molecular level is a challenging task due to the high mobility of weakly interacting solvent molecules which requires configurational sampling. For instance, polar and protic solvents can…

Chemical Physics · Physics 2025-10-22 Paul L. Türtscher , Markus Reiher