Wang–Landau Reaction Ensemble Method: Simulation of Weak Polyelectrolytes and General Acid–Base Reactions

We present a novel method for the study of weak polyelectrolytes and general acid–base reactions in molecular dynamics and Monte Carlo simulations. The approach combines the advantages of the reaction ensemble and the Wang–Landau sampling method. Deprotonation and protonation reactions are simulated...

Full description

Saved in:
Bibliographic Details
Published in:Journal of chemical theory and computation 2017-02, Vol.13 (2), p.852-862
Main Authors: Landsgesell, Jonas, Holm, Christian, Smiatek, Jens
Format: Article
Language:English
Subjects:
Accuracy
Computation
Computer simulation
Estimates
Mathematical analysis
Molecular dynamics
Monte Carlo methods
Sampling
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:We present a novel method for the study of weak polyelectrolytes and general acid–base reactions in molecular dynamics and Monte Carlo simulations. The approach combines the advantages of the reaction ensemble and the Wang–Landau sampling method. Deprotonation and protonation reactions are simulated explicitly with the help of the reaction ensemble method, while the accurate sampling of the corresponding phase space is achieved by the Wang–Landau approach. The combination of both techniques provides a sufficient statistical accuracy such that meaningful estimates for the density of states and the partition sum can be obtained. With regard to these estimates, several thermodynamic observables like the heat capacity or reaction free energies can be calculated. We demonstrate that the computation times for the calculation of titration curves with a high statistical accuracy can be significantly decreased when compared to the original reaction ensemble method. The applicability of our approach is validated by the study of weak polyelectrolytes and their thermodynamic properties.
ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.6b00791