Mechanical and thermodynamic routes to the liquid-liquid interfacial tension and mixing free energy by molecular dynamics

Ogawa, Rei; Kusudo, Hiroki; Omori, Takeshi; Smith, R. Edward; Joly, Laurent; Merabia, Samy; Yamaguchi, Yasutaka

doi:https://doi.org/10.1063/5.0238862

Mechanical and thermodynamic routes to the liquid-liquid interfacial tension and mixing free energy by molecular dynamics

Ogawa, Rei; Kusudo, Hiroki; Omori, Takeshi et al.

Journal of Chemical Physics, 2024, 161, 224708

Number of Access:391（2025-08-14 01:47 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/99699

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Title	Mechanical and thermodynamic routes to the liquid-liquid interfacial tension and mixing free energy by molecular dynamics
Creator	CreatorName Ogawa, Rei
	CreatorName Kusudo, Hiroki
	NRID 1000070467546 1000070467546 ORCID 0000-0002-7584-916X 0000-0002-7584-916X researchmap permalink takeshi_omori takeshi_omori CreatorName Omori, Takeshi
	CreatorName Smith, R. Edward
	CreatorName Joly, Laurent
	CreatorName Merabia, Samy
	NRID 1000030346192 1000030346192 ORCID 0000-0002-8000-8437 0000-0002-8000-8437 researchmap permalink yasutaka_yamaguchi yasutaka_yamaguchi Scopus Author ID 15849815900 15849815900 CreatorName Yamaguchi, Yasutaka
Description	Ogawa R et al., J. Chem. Phys. 161, 224708 (2024) https://doi.org/10.1063/5.0238862.
Abstract	In this study, we carried out equilibrium molecular dynamics (EMD) simulations of the liquid-liquid (LL) interface between two different Lennard-Jones components with varying miscibility, where we examined the relation between the interfacial tension and the free energy to completely isolate the two liquids using both a mechanical and thermodynamic approach. Using the mechanical approach, we obtained a stress distribution around a quasi-one-dimensional EMD system with a flat LL interface. From the stress distribution, we calculated the LL interfacial tension based on Bakker’s equation, which uses the stress anisotropy around the interface, and measured how it varied with miscibility. The second approach uses thermodynamic integration by enforcing quasi-static isolation of the two liquids to calculate the free energy. This uses the same EMD systems as the mechanical approach, with both extended dry-surface and phantom-wall (PW) schemes applied. When the two components were immiscible, the mechanical interfacial tension and isolation free energy were in good agreement. When the components were miscible, the values were significantly different. From the result of PW for the case of completely mixed liquids, the difference was attributed to the additional free energy required to separate the binary mixture into single components against the osmotic pressure prior to the complete detachment of the two components. This provides a new route to obtain the free energy of mixing.
Publisher	American Institute of Physics
Source Title	Journal of Chemical Physics
Volume (Issue)	161
Page	224708
Date of Issued	2024-12-14
Language	English
Handle URL	https://hdl.handle.net/11094/99699
PISSN	00219606
eISSN	10897690
Relation.isIdenticalTo	DOI (Publisher Version) https://doi.org/10.1063/5.0238862
Access Rights	open access
CopyRight	This article is licensed under a Creative Commons Attribution 4.0 International License.
oaire:version	Version of Record
Category	学術雑誌論文 Journal Article

Resource Type	journal article
Local Type	Journal Article
DCTERMS.bibliographicCitation	Journal of Chemical Physics. 2024, 161, p. 224708
DC.title	Mechanical and thermodynamic routes to the liquid-liquid interfacial tension and mixing free energy by molecular dynamics
DC.creator	Ogawa, Rei
	Kusudo, Hiroki
	Omori, Takeshi
	Smith, R. Edward
	Joly, Laurent
	Merabia, Samy
	Yamaguchi, Yasutaka
DC.publisher	American Institute of Physics
DC.language' scheme='DCTERMS.RFC1766	English
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2024-12-14
DC.identifier	https://doi.org/10.1063/5.0238862
DC.description	Ogawa R et al., J. Chem. Phys. 161, 224708 (2024) https://doi.org/10.1063/5.0238862.
DCTERMS.abstract	In this study, we carried out equilibrium molecular dynamics (EMD) simulations of the liquid-liquid (LL) interface between two different Lennard-Jones components with varying miscibility, where we examined the relation between the interfacial tension and the free energy to completely isolate the two liquids using both a mechanical and thermodynamic approach. Using the mechanical approach, we obtained a stress distribution around a quasi-one-dimensional EMD system with a flat LL interface. From the stress distribution, we calculated the LL interfacial tension based on Bakker’s equation, which uses the stress anisotropy around the interface, and measured how it varied with miscibility. The second approach uses thermodynamic integration by enforcing quasi-static isolation of the two liquids to calculate the free energy. This uses the same EMD systems as the mechanical approach, with both extended dry-surface and phantom-wall (PW) schemes applied. When the two components were immiscible, the mechanical interfacial tension and isolation free energy were in good agreement. When the components were miscible, the values were significantly different. From the result of PW for the case of completely mixed liquids, the difference was attributed to the additional free energy required to separate the binary mixture into single components against the osmotic pressure prior to the complete detachment of the two components. This provides a new route to obtain the free energy of mixing.
DC.rights	This article is licensed under a Creative Commons Attribution 4.0 International License.
DC.format	99699
citation_title	Mechanical and thermodynamic routes to the liquid-liquid interfacial tension and mixing free energy by molecular dynamics
citation_author	Ogawa, Rei
	Kusudo, Hiroki
	Omori, Takeshi
	Smith, R. Edward
	Joly, Laurent
	Merabia, Samy
	Yamaguchi, Yasutaka
citation_publisher	American Institute of Physics
citation_language	English
citation_date	2024-12-14
citation_journal_title	Journal of Chemical Physics
citation_volume	161
citation_firstpage	224708
citation_doi	https://doi.org/10.1063/5.0238862
citation_public_url	https://hdl.handle.net/11094/99699

Mechanical and thermodynamic routes to the liquid-liquid interfacial tension and mixing free energy by molecular dynamics

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