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

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.