title: Partial molar enthalpies and reaction enthalpies from equilibrium molecular dynamics simulation.
abstract: 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.
authors.affiliation: Process and Energy Laboratory, Delft University of Technology, Leeghwaterstraat 39, 2628CB Delft, The Netherlands.
authors.forename: Sondre K
authors.initials: SK
authors.lastname: Schnell
authors.affiliation: Department of Chemistry, Faculty of Natural Science and Technology, Norwegian University of Science and Technology, 4791 Trondheim, Norway.
authors.forename: Ragnhild
authors.initials: R
authors.lastname: Skorpa
authors.affiliation: Department of Chemistry, Faculty of Natural Science and Technology, Norwegian University of Science and Technology, 4791 Trondheim, Norway.
authors.forename: Dick
authors.initials: D
authors.lastname: Bedeaux
authors.affiliation: Department of Chemistry, Faculty of Natural Science and Technology, Norwegian University of Science and Technology, 4791 Trondheim, Norway.
authors.forename: Signe
authors.initials: S
authors.lastname: Kjelstrup
authors.affiliation: Process and Energy Laboratory, Delft University of Technology, Leeghwaterstraat 39, 2628CB Delft, The Netherlands.
authors.forename: Thijs J H
authors.initials: TJ
authors.lastname: Vlugt
authors.affiliation: Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303, CNRS-Université de Bourgogne, 9, av. Savary, 21000 Dijon, France.
authors.forename: Jean-Marc
authors.initials: JM
authors.lastname: Simon