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Accurately modeling photochemical reactions is difficult due to the presence of conical intersections and locally avoided crossings as well as the inherently multiconfigurational character of excited states. As such, one needs a multi-state…

Chemical Physics · Physics 2024-04-26 Matthew R. Hennefarth , Matthew R. Hermes , Donald G. Truhlar , Laura Gagliardi

We present a molecular simulation method to simultaneously find multiple transition pathways, and their associated free-energy profiles. The scheme extends path-metadynamics (PMD) [Phys. Rev. Lett. 109, 020601 (2012)] with multiple paths…

Statistical Mechanics · Physics 2025-06-23 Alberto Pérez de Alba Ortíz , Bernd Ensing

Within the frame of an effective, coarse-grained hydrophobic-polar protein model, we employ multicanonical Monte Carlo simulations to investigate free-energy landscapes and folding channels of exemplified heteropolymer sequences, which are…

Soft Condensed Matter · Physics 2009-11-13 Stefan Schnabel , Michael Bachmann , Wolfhard Janke

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…

Computational Physics · Physics 2018-11-15 Pengfei Li , Xiangyu Jia , Xiaoliang Pan , Yihan Shao , Ye Mei

Recent advances in non-equilibrium statistical mechanics and single molecule technologies make it possible to extract free energy differences from irreversible work measurements in pulling experiments. To date, free energy recovery has been…

Biological Physics · Physics 2013-04-04 Anna Alemany , Alessandro Mossa , Ivan Junier , Felix Ritort

Properties of the free energy landscape in phase space of a dense hard sphere system characterized by a discretized free energy functional of the Ramakrishnan-Yussouff form are investigated numerically. A considerable number of glassy local…

Disordered Systems and Neural Networks · Physics 2009-10-31 Chandan Dasgupta , Oriol T. Valls

Kinetic proofreading mechanisms explain the extraordinary accuracy observed in central biological events in terms of the enhanced specificity of substrate selection networks under a nonequilibrium environment. The nonequilibrium steady…

Adaptation and Self-Organizing Systems · Physics 2022-06-29 Premashis Kumar , Kinshuk Banerjee , Gautam Gangopadhyay

Simulating transition dynamics between metastable states is a fundamental challenge in dynamical systems and stochastic processes with wide real-world applications in understanding protein folding, chemical reactions and neural activities.…

Machine Learning · Computer Science 2024-10-22 Haibo Wang , Yuxuan Qiu , Yanze Wang , Rob Brekelmans , Yuanqi Du

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

We study the kinetics of crystallization in deeply supercooled liquid silicon employing computer simulations and the Stillinger-Weber three body potential. The free energy barriers to crystallisation are computed using umbrella sampling…

Soft Condensed Matter · Physics 2024-06-19 Yagyik Goswami , Vishwas V. Vasisht , Daan Frenkel , Pablo G. Debenedetti , Srikanth Sastry

Phase diagrams are an invaluable tool for material synthesis and provide information on the phases of the material at any given thermodynamic condition. Conventional phase diagram generation involves experimentation to provide an initial…

We present an ab initio approach for evaluating a free energy profile along a reaction coordinate by combining logarithmic mean force dynamics (LogMFD) and first-principles molecular dynamics. The mean force, which is the derivative of the…

Chemical Physics · Physics 2014-05-29 Makoto Nakamura , Masao Obata , Tetsuya Morishita , Tatsuki Oda

A novel and powerful method is presented for the study of rare switching events in complex systems with multiscale energy landscapes. The method performs an umbrella sampling of the equilibrium distribution of the system in hyperplanes…

Condensed Matter · Physics 2007-05-23 Weinan E , Weiqing Ren , Eric Vanden-Eijnden

Free-energy differences between pairs of end-states can be estimated based on molecular dynamics (MD) simulations using standard pathway-dependent methods such as thermodynamic integration (TI), free-energy perturbation, or Bennett's…

We introduce and analyze free energy landscapes defined by associating to any point inside the sphere a free energy calculated on a thin spherical band around it, using many orthogonal replicas. This allows us to reinterpret, rigorously…

Probability · Mathematics 2023-05-23 Eliran Subag

Existing adaptive bias techniques, which seek to estimate free energies and physical properties from molecular simulations, are limited by their reliance on fixed kernels or basis sets which hinder their ability to efficiently conform to…

Statistical Mechanics · Physics 2018-04-04 Hythem Sidky , Jonathan K. Whitmer

We train an equivariant machine learning model to predict energies and forces for a real-world study of hydrogen combustion under conditions of finite temperature and pressure. This challenging case for reactive chemistry illustrates that…

Chemical Physics · Physics 2023-06-16 Xingyi Guan , Joseph Heindel , Taehee Ko , Chao Yang , Teresa Head-Gordon

In the current AFM experiments the distribution of unfolding times, P(t), is measured by applying a constant stretching force f_s from which the apparent unfolding rate is obtained. To describe the complexity of the underlying energy…

Soft Condensed Matter · Physics 2009-11-11 V. Barsegov , D. Klimov , D. Thirumalai

In this article, we carry out a study of long-term behavior of reaction-diffusion systems augmented with self- and cross-diffusion, using an augmented Gray-Scott system as a general example. The methodology remains generic, and is therefore…

Pattern Formation and Solitons · Physics 2023-08-16 Benjamin Aymard

Inspired by thermodynamic integration, we propose a method for the calculation of time-independent free energy profiles from history-dependent biased simulations via Mean Force Integration (MFI). MFI circumvents the need for computing the…

Statistical Mechanics · Physics 2020-01-08 Veselina Marinova , Matteo Salvalaglio