Kirkwood-Buff Integrals Using Molecular Simulation: Estimation of Surface Effects

Dawass, Noura; Krüger, Peter; Schnell, Sondre K.; Moultos, Othonas A.; Economou, Ioannis G.; Vlugt, Thijs J. H.; Simon, Jean-Marc

doi:10.3390/nano10040771

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Kirkwood-Buff Integrals Using Molecular Simulation: Estimation of Surface Effects

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

Graduate School of Engineering and Molecular Chirality Research Center, Chiba University, Chiba 263-8522, Japan

Department of Materials Science and Engineering, NTNU, N-7491 Trondheim, Norway

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National Center for Scientific Research Demokritos, Institute of Nanoscience and Nanotechnology, Molecular Thermodynamics and Modelling of Materials Laboratory, GR 153 10 Aghia Paraskevi Attikis, Greece

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Chemical Engineering Program, Texas A&M University at Qatar, Education City, Doha PO Box 23874, Qatar

⁶

ICB, UMR 6303 CNRS-Université de Bourgogne, F-21078 Dijon, France

Author to whom correspondence should be addressed.

Nanomaterials 2020, 10(4), 771; https://doi.org/10.3390/nano10040771

Received: 13 March 2020 / Revised: 6 April 2020 / Accepted: 13 April 2020 / Published: 16 April 2020

(This article belongs to the Special Issue Nanoscale Thermodynamics)

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Abstract

Kirkwood-Buff (KB) integrals provide a connection between microscopic properties and thermodynamic properties of multicomponent fluids. The estimation of KB integrals using molecular simulations of finite systems requires accounting for finite size effects. In the small system method, properties of finite subvolumes with different sizes embedded in a larger volume can be used to extrapolate to macroscopic thermodynamic properties. KB integrals computed from small subvolumes scale with the inverse size of the system. This scaling was used to find KB integrals in the thermodynamic limit. To reduce numerical inaccuracies that arise from this extrapolation, alternative approaches were considered in this work. Three methods for computing KB integrals in the thermodynamic limit from information of radial distribution functions (RDFs) of finite systems were compared. These methods allowed for the computation of surface effects. KB integrals and surface terms in the thermodynamic limit were computed for Lennard–Jones (LJ) and Weeks–Chandler–Andersen (WCA) fluids. It was found that all three methods converge to the same value. The main differentiating factor was the speed of convergence with system size L. The method that required the smallest size was the one which exploited the scaling of the finite volume KB integral multiplied by L. The relationship between KB integrals and surface effects was studied for a range of densities. View Full-Text

Keywords: nanothermodynamics; Kirkwood-Buff integrals; surface effects; molecular dynamics

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MDPI and ACS Style

Dawass, N.; Krüger, P.; Schnell, S.K.; Moultos, O.A.; Economou, I.G.; Vlugt, T.J.H.; Simon, J.-M. Kirkwood-Buff Integrals Using Molecular Simulation: Estimation of Surface Effects. Nanomaterials 2020, 10, 771. https://doi.org/10.3390/nano10040771

AMA Style

Dawass N, Krüger P, Schnell SK, Moultos OA, Economou IG, Vlugt TJH, Simon J-M. Kirkwood-Buff Integrals Using Molecular Simulation: Estimation of Surface Effects. Nanomaterials. 2020; 10(4):771. https://doi.org/10.3390/nano10040771

Chicago/Turabian Style

Dawass, Noura, Peter Krüger, Sondre K. Schnell, Othonas A. Moultos, Ioannis G. Economou, Thijs J.H. Vlugt, and Jean-Marc Simon. 2020. "Kirkwood-Buff Integrals Using Molecular Simulation: Estimation of Surface Effects" Nanomaterials 10, no. 4: 771. https://doi.org/10.3390/nano10040771

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