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A new simulated tempering method, which is referred to as simulated tempering umbrella sampling, for calculating the free energy of chemical reactions is proposed. First principles molecular dynamics simulations with this simulated…

Statistical Mechanics · Physics 2012-06-05 Yoshiharu Mori , Yuko Okamoto

Correlation effects of an electron gas in an external potential are derived using an Effective Action functional method. Corrections beyond the random phase approximation (RPA) are naturally incorporated by this method. The Effective Action…

Materials Science · Physics 2009-11-10 A. Rebei , W. N. G. Hitchon

We investigate relations between spatial properties of the free energy and the radius of Gaussian curvature of the underlying curved lattice geometries. For this purpose we derive recurrence relations for the analysis of the free energy…

Statistical Mechanics · Physics 2016-06-02 Marcel Serina , Jozef Genzor , Yoju Lee , Andrej Gendiar

We present a first principles-quality potential energy surface (PES) describing the inter-atomic forces for hydrogen atoms interacting with free-standing graphene. The PES is a high-dimensional neural network potential that has been…

The temperature dependence of the rate of the reaction CH_4+H \to CH_3+H_2 is studied using classical collision theory with a temperature-dependent effective potential derived from a path integral analysis. Analytical expressions are…

Chemical Physics · Physics 2016-09-08 David Z. Goodson , Dustin W. Roelse , Wan-Ting Chiang , Steven M. Valone , J. D. Doll

Methane autothermal reforming has been studied using comprehensive, detailed microkinetic mechanisms, and a hierarchically reduced rate expression has been derived without apriori assumptions. The microkinetic mechanism is adapted from…

Materials Science · Physics 2016-01-26 Marm Dixit , Renika Baruah , Dhrupad Parikh , Sudhanshu Sharma , Atul Bhargav

Using molecular simulation, we study the nucleation of liquid droplets from binary mixtures and determine the free energy of nucleation along entropic pathways. To this aim, we develop the $\mu_1 \mu_2 VT-S$ method, based on the…

Soft Condensed Matter · Physics 2021-08-25 Caroline Desgranges , Jerome Delhommelle

Designing reaction pathways that maximize the production of a target compound in a given metabolic network is a fundamental problem in systems biology. In this study, we systematically explore the non-oxidative glycolysis metabolic network,…

Molecular Networks · Quantitative Biology 2025-06-25 Adittya Pal

In this paper, we present a study on how to develop an efficient multiscale simulation strategy for the dynamics of chemically active systems on low-dimensional supports. Such reactions are encountered in a wide variety of situations,…

Computational Physics · Physics 2015-06-04 Giacomo Mazzi , Yannick De Decker , Giovanni Samaey

In this paper we study the dissipative effects and decoherence induced on a particle moving at constant speed in front of a dielectric plate in quantum vacuum, developing a Closed-Time-Path (CTP) integral formulation in order to account for…

Quantum Physics · Physics 2019-05-22 Ludmila Viotti , M. Belén Farías , Paula I. Villar , Fernando C. Lombardo

Popular methods for identifying transition paths between energy minima, such as the nudged elastic band and string methods, typically do not incorporate potential energy curvature information, leading to slow relaxation to the minimum…

Computational Physics · Physics 2019-03-11 Stela Makri , Christoph Ortner , James R. Kermode

Various methods achieving importance sampling in ensembles of nonequilibrium trajectories enable to estimate free energy differences and, by maximum-likelihood post-processing, to reconstruct free energy landscapes. Here, based on Bayes…

Statistical Mechanics · Physics 2010-07-02 Manuel Athènes , Mihai-Cosmin Marinica

A general approach to calculate the diabatic surfaces for electron-transfer reactions is presented, based on first-principles molecular dynamics of the active centers and their surrounding medium. The excitation energy corresponding to the…

Materials Science · Physics 2009-11-11 P. H. -L. Sit , Matteo Cococcioni , Nicola Marzari

{\em Ab initio} techniques based on density functional theory in the projector-augmented-wave implementation are used to calculate the free energy and a range of other thermodynamic properties of liquid iron at high pressures and…

Materials Science · Physics 2009-11-07 D. Alfe` , G. D. Price , M. J. Gillan

Experiments are starting to probe collisions and chemical reactions between atoms and molecules at ultra-low temperatures. We have developed a new theoretical procedure for studying these collisions using the R-matrix method. Here this…

Chemical Physics · Physics 2018-10-09 Tom Rivlin , Laura K. McKemmish , Jonathan Tennyson

Finding complex reaction and transformation pathways, involving many intermediate states, is in general not possible on the DFT level with existing simulation methods due to the very large number of required energy and force evaluations.…

Computational Physics · Physics 2019-11-20 Deb Sankar De , Marco Krummenacher , Bastian Schaefer , Stefan Goedecker

We explore the recently introduced $\eta$-ensemble approach to compute the free energy directly from \emph{ab initio} path integral Monte Carlo (PIMC) simulations [T.~Dornheim \emph{et al.}, arXiv:2407.01044] and apply it to the archetypal…

Chemical Physics · Physics 2024-12-19 Tobias Dornheim , Panagiotis Tolias , Zhandos Moldabekov , Jan Vorberger

The fission processes of thermal excited nuclei are conventionally studied by statistical models which rely on inputs of phenomenological level densities and potential barriers. Therefore the microscopic descriptions of spontaneous fission…

Nuclear Theory · Physics 2016-09-14 Yi Zhu , Junchen Pei

We present in this paper the main structural features and enthalpy details for the energy profiles of the title reactions, both for the exothermic (forward) path to NH$_{3}$ formation and for the endothermic (reverse) reaction to…

Chemical Physics · Physics 2020-10-30 F. A. Gianturco , E. Yurtsever , M. Satta , R. Wester

The equilibrium free energy landscape of off-lattice model heteropolymers as a function of an internal coordinate, namely the end-to-end distance, is reconstructed from out-of-equilibrium steered molecular dynamics data. This task is…

Statistical Mechanics · Physics 2008-09-17 Stefano Luccioli , Alberto Imparato , Alessandro Torcini