6533b859fe1ef96bd12b81ef
RESEARCH PRODUCT
Partial molar enthalpies and reaction enthalpies from equilibrium molecular dynamics simulation
Sondre K. SchnellSigne KjelstrupThijs J. H. VlugtJean-marc SimonRagnhild SkorpaDick Bedeauxsubject
Molecular dynamicsChemistryThermodynamic limitEnthalpyGeneral Physics and AstronomyParticleBinary numberThermodynamicsMolecular simulationPhysical and Theoretical ChemistryChemical equilibriumChemical reactiondescription
We present a new molecular simulation technique for determining partial molar enthalpies in mixtures of gases and liquids from single simulations, without relying on particle insertions, deletions, or identity changes. The method can also be applied to systems with chemical reactions. We demonstrate our method for binary mixtures of Weeks-Chandler-Anderson particles by comparing with conventional simulation techniques, as well as for a simple model that mimics a chemical reaction. The method considers small subsystems inside a large reservoir (i.e., the simulation box), and uses the construction of Hill to compute properties in the thermodynamic limit from small-scale fluctuations. Results obtained with the new method are in excellent agreement with those from previous methods. Especially for modeling chemical reactions, our method can be a valuable tool for determining reaction enthalpies directly from a single MD simulation.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2014-10-10 |