System-size corrections for self-diffusion coefficients calculated from molecular dynamics simulations

The case of CO2, n -alkanes, and poly(ethylene glycol) dimethyl ethers

Othonas A. Moultos, Yong Zhang, Ioannis N. Tsimpanogiannis, Ioannis Economou, Edward J. Maginn

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

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.

Original languageEnglish
Article number074109
JournalJournal of Chemical Physics
Volume145
Issue number7
DOIs
Publication statusPublished - 21 Aug 2016

Fingerprint

Alkanes
alkanes
Molecular dynamics
glycols
ethers
ethylene
diffusion coefficient
molecular dynamics
Computer simulation
simulation
Propane
Methane
propane
diffusivity
methane
Thermodynamics
thermodynamics
poly(ethylene glycol) dimethyl ether
predictions

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

System-size corrections for self-diffusion coefficients calculated from molecular dynamics simulations : The case of CO2, n -alkanes, and poly(ethylene glycol) dimethyl ethers. / Moultos, Othonas A.; Zhang, Yong; Tsimpanogiannis, Ioannis N.; Economou, Ioannis; Maginn, Edward J.

In: Journal of Chemical Physics, Vol. 145, No. 7, 074109, 21.08.2016.

Research output: Contribution to journalArticle

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