RT Journal Article
T1 Density functional theory for the prediction of interfacial properties of molecular fluids within the SAFT-g coarse-grained approach
A1 Algaba Fernández, Jesús
A1 Mendiboure, Bruno
A1 Gómez Álvarez, Paula
A1 Jiménez Blas, Felipe
A1 Gómez Álvarez, Paula
AB Recently, we have proposed the SAFT-VR Mie MF DFT approach [Algaba et al., Phys. Chem. Chem. Phys., 2019, 21, 11937–11948] to investigate systems that exhibit fluid–fluid interfaces. This formalism is based on the combination of the Statistical Associating Fluid Theory for attractive potentials of variable range using Mie intermolecular potential (SAFT-VR Mie) and a Density Functional Theory (DFT) treatment of the free energy. A mean-field approach is used to evaluate the attractive term, neglecting the pair correlations associated to attractions. This theory has been combined with reported SAFT-γ Coarse-Grained (CG) Mie force fields to provide an excellent description of the vapor–liquid interface of carbon dioxide and water pure fluids. The present work is a natural and necessary extension of this previous study. We assess the adequacy of the proposed methodology for dealing with inhomogeneous fluid systems of large complex molecules, in particular carbon tetrafluoride and sulfur hexafluoride greenhouse gases, the refrigerant 2,3,3,3-tetrafluoro-1-propene, and the long-chain n-decane and n-eicosane hydrocarbons. The obvious diversity of these fluids, their chemical and industrial interest, and the fact of that SAFT-γ CG Mie force fields have been reported for them justify such choice. With the aim of testing the theory, we perform Molecular Dynamics simulations in the canonical ensemble using the direct coexistence technique for the same models. We focus both on bulk, such as coexistence diagrams and vapor pressure curves, as well as interfacial properties, including surface tension. The comparison of the theoretical predictions with the computational results as well as with experimental data taken from the literature demonstrates the reliability and generalization of this method for dealing simultaneously with vapor–liquid equilibrium and interfacial phenomena. Hence, it appears as a potential tool for the interface analysis, with the main advantage over molecular simulation of low computational cost, and solving the experimental difficulties in accurately measuring the surface tension of certain systems.
PB Royal Society of Chemistry
SN 2046-2069 (electrónico)
YR 2022
FD 2022
LK http://hdl.handle.net/10272/21065
UL http://hdl.handle.net/10272/21065
LA eng
NO Algaba, J., Mendiboure, B., Gómez-Álvarez, P., & Blas, F. J. (2022). Density functional theory for the prediction of interfacial properties of molecular fluids within the SAFT-γ coarse-grained approach. In RSC Advances (Vol. 12, Issue 29, pp. 18821–18833). Royal Society of Chemistry (RSC). https://doi.org/10.1039/d2ra02162e
NO This work was nanced by Spanish Ministerio de Econom´ıa,Industria y Competitividad (Grant No. FIS2017-89361-C3-1-P),Spanish Ministerio de Ciencia e Innovaci´on (Grant No.PID2021-125081NB-I00), Junta de Andaluc´ıa (Grant No. P20-00363), both co-nanced by EU FEDER funds, and Universidadde Huelva. We also acknowledge the Centro deSupercomputaci´on de Galicia (CESGA, Santiago de Compostela,Spain) for providing access to computing facilities.
DS Repositorio Institucional de la Universidad de Huelva
RD 31 may 2026