System-size corrections for self-diffusion coefficients calculated from molecular dynamics simulations: The case of CO2, n-alkanes, and poly(ethylene glycol) dimethyl ethers

被引：106

作者：

Moultos, Othonas A. ^{[1
]}

Zhang, Yong ^{[2
]}

Tsimpanogiannis, Ioannis N. ^{[1
,3
]}

Economou, Ioannis G. ^{[1
]}

Maginn, Edward J. ^{[2
]}

机构：

[1] Texas A&M Univ, Chem Engn Program, POB 23847, Doha, Qatar

[2] Univ Notre Dame, Dept Chem & Biomol Engn, Notre Dame, IN 46556 USA

[3] Natl Ctr Sci Res Demokritos, Environm Res Lab, Aghia Paraskevi 15310, Greece

来源：

JOURNAL OF CHEMICAL PHYSICS | 2016年 / 145卷 / 07期

关键词：

UNITED-ATOM DESCRIPTION; PARTICLE MESH EWALD; TRANSFERABLE POTENTIALS; INITIAL CONFIGURATIONS; PHASE-EQUILIBRIA; CARBON-DIOXIDE; FORCE-FIELD; HARD-SPHERE; VISCOSITY; TEMPERATURE;

D O I：

10.1063/1.4960776

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Molecular dynamics simulations were carried out to study the self-diffusion coefficients of CO2, methane, propane, n-hexane, n-hexadecane, and various poly(ethylene glycol) dimethyl ethers (glymes in short, CH3O-(CH2CH2O)(n)-CH3 with n = 1, 2, 3, and 4, labeled as G1, G2, G3, and G4, respectively) at different conditions. Various system sizes were examined. The widely used Yeh and Hummer [J. Phys. Chem. B 108, 15873 (2004)] correction for the prediction of diffusion coefficient at the thermodynamic limit was applied and shown to be accurate in all cases compared to extrapolated values at infinite system size. The magnitude of correction, in all cases examined, is significant, with the smallest systems examined giving for some cases a self-diffusion coefficient approximately 15% lower than the infinite system-size extrapolated value. The results suggest that finite size corrections to computed self-diffusivities must be used in order to obtain accurate results. Published by AIP Publishing.

引用

页数：6