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Title: Performance of density functionals for modeling vapor liquid equilibria of CO 2 and SO 2

Abstract

Vapor liquid equilibria (VLE) and condensed phase properties of carbon dioxide and sulfur dioxide are calculated using first principles Monte Carlo (FPMC) simulations to assess the performance of several density functionals, notably PBE-D3, BLYP-D3,PBE0-D3, M062X-D3, and rVV10. GGA functionals were used to compute complete vapor liquid coexistence curves (VLCCs) to estimate critical properties, while the hybrid and nonlocal vander Waals functionals were used only for computing density at a single state point due to the high computational cost. Our results show that the BLYP-D3 functional performs well in predicting VLE properties for both molecules when compared with other functionals. In the liquid phase, pair correlation functions reveal that there is not a significant difference in the location of the peak for the first solvation shell while the peak heights are different for different functionals. Altogether, theBLYP-D3 functional is a good choice for modeling VLE of acidic gases with significant environmental implications such as CO 2 and SO 2.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
  1. Mississippi State Univ., Mississippi State, MS (United States). Dave C. Swalm School of Chemical Engineering, and Center for Advanced Vehicular Systems
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory, Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC).
Sponsoring Org.:
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR) (SC-21)
OSTI Identifier:
1461662
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Computational Chemistry
Additional Journal Information:
Journal Volume: 39; Journal Issue: 8; Journal ID: ISSN 0192-8651
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; first principles Monte Carlo; dispersion; vapor liquid equilibria; CO2; SO2; density functional theory

Citation Formats

Goel, Himanshu, Windom, Zachary W., Jackson, Amber A., and Rai, Neeraj. Performance of density functionals for modeling vapor liquid equilibria of CO2 and SO2. United States: N. p., 2017. Web. doi:10.1002/jcc.25123.
Goel, Himanshu, Windom, Zachary W., Jackson, Amber A., & Rai, Neeraj. Performance of density functionals for modeling vapor liquid equilibria of CO2 and SO2. United States. doi:10.1002/jcc.25123.
Goel, Himanshu, Windom, Zachary W., Jackson, Amber A., and Rai, Neeraj. Tue . "Performance of density functionals for modeling vapor liquid equilibria of CO2 and SO2". United States. doi:10.1002/jcc.25123. https://www.osti.gov/servlets/purl/1461662.
@article{osti_1461662,
title = {Performance of density functionals for modeling vapor liquid equilibria of CO2 and SO2},
author = {Goel, Himanshu and Windom, Zachary W. and Jackson, Amber A. and Rai, Neeraj},
abstractNote = {Vapor liquid equilibria (VLE) and condensed phase properties of carbon dioxide and sulfur dioxide are calculated using first principles Monte Carlo (FPMC) simulations to assess the performance of several density functionals, notably PBE-D3, BLYP-D3,PBE0-D3, M062X-D3, and rVV10. GGA functionals were used to compute complete vapor liquid coexistence curves (VLCCs) to estimate critical properties, while the hybrid and nonlocal vander Waals functionals were used only for computing density at a single state point due to the high computational cost. Our results show that the BLYP-D3 functional performs well in predicting VLE properties for both molecules when compared with other functionals. In the liquid phase, pair correlation functions reveal that there is not a significant difference in the location of the peak for the first solvation shell while the peak heights are different for different functionals. Altogether, theBLYP-D3 functional is a good choice for modeling VLE of acidic gases with significant environmental implications such as CO2 and SO2.},
doi = {10.1002/jcc.25123},
journal = {Journal of Computational Chemistry},
number = 8,
volume = 39,
place = {United States},
year = {2017},
month = {11}
}

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Cited by: 5 works
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Figures / Tables:

Figure 1 Figure 1: Potential energy curves of CO2 with different functionals for parallel displaced (top) and T configuration(bottom). The black star, red circle, blue diamond, indigo upper triangle, maroon down triangle, orange squares, and green left triangle symbols represent data obtained from the CCSD(T)/aVTZ (aug-cc-pVTZ) level of theory, BLYP-D3/PW (Plane wave),more » PBE-D3/PW, PBE0-D3/PW, rVV10/PW, M062X-D3/PW, and M062XD3/ aVTZ functionals, respectively. The dashed lines of the corresponding color are guide to the eye.« less

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