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

アクセス数:387件（2025-08-01 16:52 集計）

固定URL: https://hdl.handle.net/11094/99699

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タイトル	Mechanical and thermodynamic routes to the liquid-liquid interfacial tension and mixing free energy by molecular dynamics
著者	著者名 Ogawa, Rei
	著者名 Kusudo, Hiroki
	NRID 1000070467546 1000070467546 ORCID 0000-0002-7584-916X 0000-0002-7584-916X researchmap permalink takeshi_omori takeshi_omori 著者名 Omori, Takeshi
	著者名 Smith, R. Edward
	著者名 Joly, Laurent
	著者名 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 著者名 Yamaguchi, Yasutaka
内容	Ogawa R et al., J. Chem. Phys. 161, 224708 (2024) https://doi.org/10.1063/5.0238862.
抄録	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.
出版者	American Institute of Physics
収録物名	Journal of Chemical Physics
巻(号)	161
ページ	224708
刊行年月	2024-12-14
言語	英語
ハンドルURL	https://hdl.handle.net/11094/99699
PISSN	00219606
eISSN	10897690
関連情報 (isIdenticalTo)	DOI (出版社版) https://doi.org/10.1063/5.0238862
アクセス権	open access
権利情報	This article is licensed under a Creative Commons Attribution 4.0 International License.
出版タイプ	Version of Record
カテゴリ	学術雑誌論文 Journal Article

資源タイプ	学術雑誌論文
ローカル資源タイプ	学術雑誌論文
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	英語
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	英語
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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