Generalized Form for Finite-Size Corrections in Mutual Diffusion Coefficients of Multicomponent Mixtures Obtained from Equilibrium Molecular Dynamics Simulation

Journal of Chemical Theory and Computation, vol. 16, pp. 3799–3806

Abstract

Abstract The system-size dependence of computed mutual diffusion coefficients of multicomponent mixtures is investigated, and a generalized correction term is derived. The generalized finite-size correction term was validated for the ternary molecular mixture chloroform/acetone/methanol as well as 28 ternary LJ systems. It is shown that only the diagonal elements of the Fick matrix show system-size dependency. The finite-size effects of these elements can be corrected by adding the term derived by Yeh and Hummer (J. Phys. Chem. B 2004, 108, 15873–15879). By performing an eigenvalue analysis of the finite-size effects of the matrix of Fick diffusivities we show that the eigenvector matrix of Fick diffusivities does not depend on the size of the simulation box. Only eigenvalues, which describe the speed of diffusion, depend on the size of the system. An analytic relation for finite-size effects of the matrix of Maxwell–Stefan diffusivities was developed. All Maxwell–Stefan diffusivities depend on the system size, and the required correction depends on the matrix of thermodynamic factors.

Authors 4

1. Seyed Hossein Jamali

   Delft University of Technology

   Affiliation as printed

   Delft University of Technology , , Leeghwaterstraat 39 , ,

   Engineering Thermodynamics, Process & Energy Department, Faculty of Mechanical, Maritime and Materials Engineering, Delft University of Technology, Leeghwaterstraat 39, 2628CB Delft, The Netherlands

2. André Bardow Aachen Institute of Technical Thermodynamics

   ETH Zurich · RWTH Aachen University

   Affiliation as printed

   ETH Zurich , , Tannenstrasse 3 , ,

   RWTH Aachen University , , ,

   Energy Process Systems Engineering, Department of Mechanical and Process Engineering, ETH Zurich, Tannenstrasse 3, 8092 Zürich, Switzerland

   Institute of Technical Thermodynamics, RWTH Aachen University, 52056 Aachen, Germany

3. Thijs J. H. Vlugt

   Delft University of Technology

   Affiliation as printed

   Delft University of Technology , , Leeghwaterstraat 39 , ,

   Engineering Thermodynamics, Process & Energy Department, Faculty of Mechanical, Maritime and Materials Engineering, Delft University of Technology, Leeghwaterstraat 39, 2628CB Delft, The Netherlands

4. Othonas A. Moultos corresponding

   Delft University of Technology

   Affiliation as printed

   Delft University of Technology , , Leeghwaterstraat 39 , ,

   Engineering Thermodynamics, Process & Energy Department, Faculty of Mechanical, Maritime and Materials Engineering, Delft University of Technology, Leeghwaterstraat 39, 2628CB Delft, The Netherlands