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Ab initio development of generalized Lennard-Jones (Mie) force fields for predictions of thermodynamic properties in advanced molecular-based SAFT equations of state

Walker, Pierre J. and Zhao, Tianpu and Haslam, Andrew J. and Jackson, George (2022) Ab initio development of generalized Lennard-Jones (Mie) force fields for predictions of thermodynamic properties in advanced molecular-based SAFT equations of state. Journal of Chemical Physics, 156 (15). Art. No. 154106. ISSN 0021-9606. doi:10.1063/5.0087125. https://resolver.caltech.edu/CaltechAUTHORS:20220519-374865000

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Abstract

A methodology for obtaining molecular parameters of a modified statistical associating fluid theory for variable-range interactions of Mie form (SAFT-VR Mie) equation of state (EoS) from ab initio calculations is proposed for non-associative species that can be modeled as single spherical segments. The methodology provides a strategy to map interatomic or intermolecular potentials obtained from ab initio quantum-chemistry calculations to the corresponding Mie potentials that can be used within the SAFT-VR Mie EoS. The inclusion of corrections for quantum and many-body effects allows for an excellent, fully predictive description of the vapor–liquid envelope and other bulk thermodynamic properties of noble gases; this description is of similar or superior quality to that obtained using SAFT-VR Mie with parameters regressed in the traditional way using experimental thermodynamic-property data. The methodology is extended to an anisotropic species, methane, where similar levels of accuracy are obtained. The efficacy of using less-accurate quantum-chemistry methods in this methodology is explored, showing that these methods do not provide satisfactory results, although we note that the description is nevertheless substantially better than those obtained using the conductor-like screening model for describing real solvents (COSMO-RS), the only other fully predictive ab initio method currently available. Overall, the reliance on thermophysical data is completely dispensed with, providing the first extensible, wholly predictive SAFT-type EoSs.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1063/5.0087125DOIArticle
https://aip.scitation.org/doi/suppl/10.1063/5.0087125/suppl_file/supplementary_material.pdfPublisherSupporting Information
https://github.com/pw0908/ORCA_SAFTRelated ItemCodes and data
https://github.com/ypaul21/Clapeyron.jl/blob/master/examples/user_defined_eos.ipynbRelated Iteminput scripts for calculations with SAFT-VR Mie and its variants
ORCID:
AuthorORCID
Walker, Pierre J.0000-0001-8628-6561
Zhao, Tianpu0000-0001-8264-9484
Haslam, Andrew J.0000-0002-8442-119X
Jackson, George0000-0002-8029-8868
Additional Information:© 2022 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). Submitted: 01 February 2022 • Accepted: 09 March 2022 • Published Online: 18 April 2022. The authors would like to thank David Bowskill and Michele Valsecchi, Dr. Ailo Aasen, Dr. Giovanni Bistoni, and Dr. Ahmet Altun, and Professor Øivind Wilhelmsen, Professor Patrice Paricaud, and Professor Alejandro Gil-Villegas for insightful conversations; the work by Gil-Villegas and co-workers1031,04 was invaluable to us in the developing the framework of our approach. We would also like to thank Hon-Wa Yew and Professor Dr. rer. nat. Robert Hellmann for assistance during the duration of the project. We acknowledge additional support from the Engineering and Physical Sciences Research Council (EPSRC) of the United Kingdom through grants (EP/E016340 and EP/J014958) to the Molecular Systems Engineering group at Imperial College London. The authors have no conflicts to disclose. Author Contributions. P.J.W. and T.Z. contributed equally to this work. DATA AVAILABILITY. Codes and data relating to our article are available from https://github.com/pw0908/ORCA_SAFT; the input scripts for calculations with SAFT-VR Mie and its variants are available from https://github.com/ypaul21/Clapeyron.jl/blob/master/examples/user_defined_eos.ipynb.
Funders:
Funding AgencyGrant Number
Engineering and Physical Sciences Research Council (EPSRC)EP/E016340
Engineering and Physical Sciences Research Council (EPSRC)EP/J014958
Issue or Number:15
DOI:10.1063/5.0087125
Record Number:CaltechAUTHORS:20220519-374865000
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220519-374865000
Official Citation:Pierre J. Walker, Tianpu Zhao, Andrew J. Haslam, and George Jackson, "Ab initio development of generalized Lennard-Jones (Mie) force fields for predictions of thermodynamic properties in advanced molecular-based SAFT equations of state", J. Chem. Phys. 156, 154106 (2022) https://doi.org/10.1063/5.0087125
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114808
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:19 May 2022 23:26
Last Modified:19 May 2022 23:26

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