Simulation of chemical reaction equilibria by the reaction ensemble Monte Carlo method: a review†

Abstract

Understanding and predicting the equilibrium behaviour of chemically reacting systems in highly non-ideal environments is critical to many fields of science and technology, including solvation, nanoporous materials, catalyst design, combustion and propulsion science, shock physics and many more. A method with recent success in predicting the equilibrium behaviour of reactions under non-ideal conditions is the reaction ensemble Monte Carlo method (RxMC). RxMC has been applied to reactions confined in porous solids or near solid surfaces, reactions at high temperature and/or high pressure, reactions in solution and at phase interfaces. The only required information is a description of the intermolecular forces among the system molecules and standard free-energy data for the reacting components. Extensions of the original method include its combination with algorithms for systems involving phase equilibria, constant-enthalpy and constant-internal energy adiabatic conditions, a method to include reaction kinetics, a method to study the dynamics of reacting systems, and a mesoscale method to simulate long-chain molecule phase separation. This manuscript surveys the various applications and adaptations of the RxMC method to date. Additionally, the relationship between the RxMC method and other techniques that simulate chemical reaction behaviour is given, along with insight into some technical nuances not found in the pioneering papers.

Keywords:

• Monte Carlo
• reaction
• equilibria
• simulation

Acknowledgements

The authors wish to thank Professor Athanassios Z. Panagiotopoulos for insightful comments and Chethan Acharya for careful proofreading of the manuscript. KEG acknowledges support in part by an NSF GOALI grant no. CTS-0626031. ML acknowledges support by the Grant Agency of the Czech Republic (project No. 203/05/0725), by the Grant Agency of Academy of Sciences of the Czech Republic (project No. IAA400720710), by the National Research Programme ‘Information Society’ (projects No. 1ET400720507 and No. 1ET400720409), and by the Grant Programme of Academy of Sciences of the Czech Republic ‘Nanotechnology for Society’ (project No. KAN400720701). WRS acknowledges the support of the Natural Sciences and Research Council under Grant OGP1041, and the resources of the SHARCNET computing consortium (http://www.sharcnet.ca), which was used for some of the calculations. CHT acknoweldges financial support from DOE-EPSCoR grant no. DE-FG02-01ER45867 and computational resources from an MRAC/TeraGrid allocation.

Notes

^†Bill Smith's co-authors congratulate him on his 65th birthday.