Cargando…
Finite-Size Effects of Binary Mutual Diffusion Coefficients from Molecular Dynamics
[Image: see text] Molecular dynamics simulations were performed for the prediction of the finite-size effects of Maxwell-Stefan diffusion coefficients of molecular mixtures and a wide variety of binary Lennard–Jones systems. A strong dependency of computed diffusivities on the system size was observ...
Autores principales: | , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2018
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5943679/ https://www.ncbi.nlm.nih.gov/pubmed/29664633 http://dx.doi.org/10.1021/acs.jctc.8b00170 |
_version_ | 1783321676387188736 |
---|---|
author | Jamali, Seyed Hossein Wolff, Ludger Becker, Tim M. Bardow, André Vlugt, Thijs J. H. Moultos, Othonas A. |
author_facet | Jamali, Seyed Hossein Wolff, Ludger Becker, Tim M. Bardow, André Vlugt, Thijs J. H. Moultos, Othonas A. |
author_sort | Jamali, Seyed Hossein |
collection | PubMed |
description | [Image: see text] Molecular dynamics simulations were performed for the prediction of the finite-size effects of Maxwell-Stefan diffusion coefficients of molecular mixtures and a wide variety of binary Lennard–Jones systems. A strong dependency of computed diffusivities on the system size was observed. Computed diffusivities were found to increase with the number of molecules. We propose a correction for the extrapolation of Maxwell–Stefan diffusion coefficients to the thermodynamic limit, based on the study by Yeh and Hummer (J. Phys. Chem. B, 2004, 108, 15873−15879). The proposed correction is a function of the viscosity of the system, the size of the simulation box, and the thermodynamic factor, which is a measure for the nonideality of the mixture. Verification is carried out for more than 200 distinct binary Lennard–Jones systems, as well as 9 binary systems of methanol, water, ethanol, acetone, methylamine, and carbon tetrachloride. Significant deviations between finite-size Maxwell–Stefan diffusivities and the corresponding diffusivities at the thermodynamic limit were found for mixtures close to demixing. In these cases, the finite-size correction can be even larger than the simulated (finite-size) Maxwell–Stefan diffusivity. Our results show that considering these finite-size effects is crucial and that the suggested correction allows for reliable computations. |
format | Online Article Text |
id | pubmed-5943679 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-59436792018-05-11 Finite-Size Effects of Binary Mutual Diffusion Coefficients from Molecular Dynamics Jamali, Seyed Hossein Wolff, Ludger Becker, Tim M. Bardow, André Vlugt, Thijs J. H. Moultos, Othonas A. J Chem Theory Comput [Image: see text] Molecular dynamics simulations were performed for the prediction of the finite-size effects of Maxwell-Stefan diffusion coefficients of molecular mixtures and a wide variety of binary Lennard–Jones systems. A strong dependency of computed diffusivities on the system size was observed. Computed diffusivities were found to increase with the number of molecules. We propose a correction for the extrapolation of Maxwell–Stefan diffusion coefficients to the thermodynamic limit, based on the study by Yeh and Hummer (J. Phys. Chem. B, 2004, 108, 15873−15879). The proposed correction is a function of the viscosity of the system, the size of the simulation box, and the thermodynamic factor, which is a measure for the nonideality of the mixture. Verification is carried out for more than 200 distinct binary Lennard–Jones systems, as well as 9 binary systems of methanol, water, ethanol, acetone, methylamine, and carbon tetrachloride. Significant deviations between finite-size Maxwell–Stefan diffusivities and the corresponding diffusivities at the thermodynamic limit were found for mixtures close to demixing. In these cases, the finite-size correction can be even larger than the simulated (finite-size) Maxwell–Stefan diffusivity. Our results show that considering these finite-size effects is crucial and that the suggested correction allows for reliable computations. American Chemical Society 2018-04-17 2018-05-08 /pmc/articles/PMC5943679/ /pubmed/29664633 http://dx.doi.org/10.1021/acs.jctc.8b00170 Text en Copyright © 2018 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes. |
spellingShingle | Jamali, Seyed Hossein Wolff, Ludger Becker, Tim M. Bardow, André Vlugt, Thijs J. H. Moultos, Othonas A. Finite-Size Effects of Binary Mutual Diffusion Coefficients from Molecular Dynamics |
title | Finite-Size Effects of Binary Mutual Diffusion Coefficients
from Molecular Dynamics |
title_full | Finite-Size Effects of Binary Mutual Diffusion Coefficients
from Molecular Dynamics |
title_fullStr | Finite-Size Effects of Binary Mutual Diffusion Coefficients
from Molecular Dynamics |
title_full_unstemmed | Finite-Size Effects of Binary Mutual Diffusion Coefficients
from Molecular Dynamics |
title_short | Finite-Size Effects of Binary Mutual Diffusion Coefficients
from Molecular Dynamics |
title_sort | finite-size effects of binary mutual diffusion coefficients
from molecular dynamics |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5943679/ https://www.ncbi.nlm.nih.gov/pubmed/29664633 http://dx.doi.org/10.1021/acs.jctc.8b00170 |
work_keys_str_mv | AT jamaliseyedhossein finitesizeeffectsofbinarymutualdiffusioncoefficientsfrommoleculardynamics AT wolffludger finitesizeeffectsofbinarymutualdiffusioncoefficientsfrommoleculardynamics AT beckertimm finitesizeeffectsofbinarymutualdiffusioncoefficientsfrommoleculardynamics AT bardowandre finitesizeeffectsofbinarymutualdiffusioncoefficientsfrommoleculardynamics AT vlugtthijsjh finitesizeeffectsofbinarymutualdiffusioncoefficientsfrommoleculardynamics AT moultosothonasa finitesizeeffectsofbinarymutualdiffusioncoefficientsfrommoleculardynamics |