Effectively parameterizing dissipative particle dynamics using COSMO-SAC: A partition coefficient study.

Abstract

Dissipative Particle Dynamics (DPD) provides a tool for studying phase behavior and interfacial phenomena for complex mixtures and macromolecules. Methods to quickly and automatically parameterize DPD greatly increase its effectiveness. One such method is to map predicted activity coefficients derived from COSMO-SAC onto DPD parameter sets. However, there are serious limitations to the accuracy of this mapping, including the inability of single DPD beads to reproduce asymmetric infinite dilution activity coefficients, the loss of precision when reusing parameters for different molecular fragments, and the error due to bonding beads together. This report describes these effects in quantitative detail and provides methods to mitigate much of their deleterious effects. This includes a novel approach to remove errors caused by bonding DPD beads together. Using these methods, logarithm hexane/water partition coefficients were calculated for 61 molecules. The root mean-squared error for these calculations was determined to be 0.14-a very low value-with respect to the final mapping procedure. Cognizance of the above limitations can greatly enhance the predictive power of DPD.