Replica-Averaging: An algorithm to study mechano-reactive processes for polymers under flow conditions

TL;DR

The paper introduces a replica-averaging simulation method that improves the accuracy of predicting force-mediated polymer reactions under flow by reducing fluctuations in force profiles, outperforming traditional methods.

Contribution

A novel replica-averaging approach is developed to accurately predict mechano-reactive kinetics in polymers under flow, addressing limitations of existing Brownian dynamics simulations.

Findings

Replica-averaging reduces high fluctuation effects in force profiles.

The method more accurately predicts reaction kinetics under transient conditions.

Parameter influence on prediction accuracy is analyzed.

Abstract

A new method based on quasi-independent parallel simulations approach, replica-averaging, has been developed to study the influence of flow on mechanical force-mediated polymer processes such as denaturation and breaking of bonds. This method considerably mitigates the unphysical prediction of force-mediated events inherent in Brownian dynamics (BD) polymer chain simulations that employ instantaneous force profile-based criteria to identify the occurrence of such events. This inaccuracy in predicting force-mediated event kinetics is due to high fluctuations of the instantaneous force profile around the average force. Replica-averaging reduces such high fluctuation effects by computing a force profile that faithfully represents the average force profile of the polymer chain conformation, which is then used to predict reactive events. For transient conformation conditions, the replica-averaged method more accurately predicts mechano-reactive kinetics than the time-averaged method, typically employed to reduce the unphysical prediction of force-mediated events in BD simulations. Further, the influence of the proposed replica-averaging method parameters on the accuracy of predicting the true average force profile along the polymer is discussed.