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Predicting vapor liquid equilibria using density functional theory: a case study of argon

Goel, Himanshu; Ling, Sanliang; Ellis, Breanna Nicole; Taconi, Anna; Slater, Ben; Rai, Neeraj

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Authors

Himanshu Goel

Breanna Nicole Ellis

Anna Taconi

Ben Slater

Neeraj Rai



Abstract

Predicting vapor liquid equilibria (VLE) of molecules governed by weak van der Waals (vdW) interactions using the first principles approach is a significant challenge. Due to the poor scaling of the post Hartree-Fock wave function theory with system size/basis functions, the Kohn-Sham density functional theory (DFT) is preferred for systems with a large number of molecules. However, traditional DFT cannot adequately account for medium to long range correlations which are necessary for modeling vdW interactions. Recent developments in DFT such as dispersion corrected models and nonlocal van der Waals functionals have attempted to address this weakness with a varying degree of success. In this work, we predict the VLE of argon and assess the performance of several density functionals and the second order Møller-Plesset perturbation theory (MP2) by determining critical and structural properties via first principles Monte Carlo simulations. PBE-D3, BLYP-D3, and rVV10 functionals were used to compute vapor liquid coexistence curves, while PBE0-D3, M06-2X-D3, and MP2 were used for computing liquid density at a single state point. The performance of the PBE-D3 functional for VLE is superior to other functionals (BLYP-D3 and rVV10). At T = 85 K and P = 1 bar, MP2 performs well for the density and structural features of the first solvation shell in the liquid phase.

Citation

Goel, H., Ling, S., Ellis, B. N., Taconi, A., Slater, B., & Rai, N. (2018). Predicting vapor liquid equilibria using density functional theory: a case study of argon. Journal of Chemical Physics, 148(22), Article 224501. https://doi.org/10.1063/1.5025726

Journal Article Type Article
Acceptance Date May 24, 2018
Publication Date Jun 12, 2018
Deposit Date Jun 14, 2018
Publicly Available Date Jun 14, 2018
Journal Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher American Institute of Physics
Peer Reviewed Peer Reviewed
Volume 148
Issue 22
Article Number 224501
DOI https://doi.org/10.1063/1.5025726
Keywords Density functional theory; Vapor liquid equilibria; Dispersion interactions; First principles Monte Carlo; Liquid structure
Public URL https://nottingham-repository.worktribe.com/output/938031
Publisher URL http://dx.doi.org/10.1063/1.5025726
Additional Information This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article appeared in Himanshu Goel, Sanliang Ling, Breanna Nicole Ellis, Anna Taconi, Ben Slater, Neeraj Rai (2018) Predicting vapor liquid equilibria using density functional theory: A case study of argon. Journal of Chemical Physics v. 148, no. 2 224501 and may be found at http://dx.doi.org/10.1063/1.5025726.
Contract Date Jun 14, 2018

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