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

• Published in: Journal of chemical theory and computation Vol. 13; no. 2; pp. 852 - 862
• Main Authors: Landsgesell, Jonas, Holm, Christian, Smiatek, Jens
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 14-02-2017
• Subjects: Accuracy; Computation; Computer simulation; Estimates; Mathematical analysis; Molecular dynamics; Monte Carlo methods; Sampling
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.6b00791

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.