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Title: Partial molar enthalpies and reaction enthalpies from equilibrium molecular dynamics simulation

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:
 [1] ;  [2] ;  [3] ; ;  [4] ;  [4] ;  [5] ;  [1] ;  [6]
  1. Process and Energy Laboratory, Delft University of Technology, Leeghwaterstraat 39, 2628CB Delft (Netherlands)
  2. (United States)
  3. (Norway)
  4. Department of Chemistry, Faculty of Natural Science and Technology, Norwegian University of Science and Technology, 4791 Trondheim (Norway)
  5. (Netherlands)
  6. Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303, CNRS-Université de Bourgogne, 9, av. Savary, 21000 Dijon (France)
Publication Date:
OSTI Identifier:
22436585
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 14; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BINARY MIXTURES; CHEMICAL REACTIONS; MOLECULAR DYNAMICS METHOD; PARTICLES; REACTION HEAT; SIMULATION