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A theory for the thermodynamic properties of steps on faceted crystalline surfaces is presented. The formalism leads to the definition of step excess quantities, including an excess step stress that is the step analogy of surface stress.…

Materials Science · Physics 2017-05-03 Rodrigo Freitas , Timofey Frolov , Mark Asta

Transition path sampling (TPS) is a powerful technique for investigating rare transitions, especially when the mechanism is unknown and one does not have access to the reaction coordinate. Straightforward application of TPS does not…

Chemical Physics · Physics 2019-07-11 Z. Faidon Brotzakis , Peter G. Bolhuis

Ring polymer molecular dynamics (RPMD) has proven to be an accurate approach for calculating thermal rate coefficients of various chemical reactions. For wider application of this methodology, efficient ways to generate the underlying…

Chemical Physics · Physics 2020-01-08 Ivan S. Novikov , Alexander V. Shapeev , Yury V. Suleimanov

A multilevel approach to sample the potential energy surface in a path integral formalism is proposed. The purpose is to reduce the required number of ab initio evaluations of energy and forces in ab initio path integral molecular dynamics…

Computational Physics · Physics 2014-12-22 Hua Y. Geng

Transition states and minimum energy paths are essential to understand and predict chemical reactivity. Double-ended methods represent a standard approach for their determination. We introduce a new double-ended method that optimizes…

Chemical Physics · Physics 2020-02-18 Alain C. Vaucher , Markus Reiher

The multiple range random walk algorithm recently proposed by Wang and Landau [Phys. Rev. Lett. 86, 2050 (2001)] is adapted to the computation of free energy profiles for molecular systems along reaction coordinates. More generally, we show…

Statistical Mechanics · Physics 2009-11-07 F. Calvo

The calculation of the interfacial free energy between two thermodynamic phases is crucial across various fields, including materials science, chemistry, and condensed matter physics. In this study, we apply an existing thermodynamic…

Soft Condensed Matter · Physics 2024-11-26 Ignacio Sanchez-Burgos , Pablo Montero de Hijes , Eduardo Sanz , Carlos Vega , Jorge R. Espinosa

Identifying minimum-energy paths (MEPs) is crucial for understanding chemical reaction mechanisms but remains computationally demanding. We introduce MEPIN, a scalable machine-learning method for efficiently predicting MEPs from reactant…

Chemical Physics · Physics 2026-02-18 Juno Nam , Miguel Steiner , Max Misterka , Soojung Yang , Avni Singhal , Rafael Gómez-Bombarelli

The properties of dynamic (least action) fission paths are analyzed and compared to the ones of the more traditional static (least energy) paths. Both the BCPM and Gogny D1M energy density functionals are used in the calculation of the HFB…

Nuclear Theory · Physics 2015-06-22 Samuel A. Giuliani , Luis M. Robledo , R. Rodriguez-Guzman

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

Using the entropy $S$ as a reaction coordinate, we determine the free energy barrier associated with the formation of a liquid droplet from a supersaturated vapor for atomic and molecular fluids. For this purpose, we develop the $\mu VT-S$…

Statistical Mechanics · Physics 2021-08-25 Caroline Desgranges , Jerome Delhommelle

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

We analyze the efficiency of different methods for the calculation of reaction rates in the case of two simple analytical benchmark systems. Two classes of methods are considered: the first are based on the free energy calculation along a…

Statistical Mechanics · Physics 2009-11-11 Titus S. van Erp

Molecular dynamics is a powerful tool for studying the thermodynamics and kinetics of complex molecular events. However, these simulations can rarely sample the required time scales in practice. Transition path sampling overcomes this…

Chemical Physics · Physics 2023-07-31 Gianmarco Lazzeri , Hendrik Jung , Peter G. Bolhuis , Roberto Covino

The microscopic approach to calculating the free energy of a three-dimensional Ising-like system in a homogeneous external field is developed in the higher non-Gaussian approximation (the $\rho^6$ model) at temperatures above the critical…

Statistical Mechanics · Physics 2008-12-11 I. V. Pylyuk , M. P. Kozlovskii

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

An analytic method for deriving the free energy of a three-dimensional Ising-like system near the critical point in a homogeneous external field is developed in the $\rho^6$ model approximation. The mathematical description proposed for…

Statistical Mechanics · Physics 2007-11-21 I. V. Pylyuk

Transition state or minimum energy path finding methods constitute a routine component of the computational chemistry toolkit. Standard analysis involves trajectories conventionally plotted in terms of the relative energy to the initial…

Chemical Physics · Physics 2026-03-09 Rohit Goswami

We study the dissociative adsorption of methane at the surface of graphene. Free energy profiles, which include activation energies for different steps of the reaction, are computed from constrained ab initio molecular dynamics. At 300 K,…

Materials Science · Physics 2018-04-04 Mateusz Wlazło , Jacek A. Majewski

We propose a simple formula for fitting the electron mean free paths in solids both at high and at low electron energies. The free-electron-gas approximation used for predicting electron mean free paths is no longer valid at low energies (E…

Materials Science · Physics 2009-11-11 B. Ziaja , R. A. London , J. Hajdu