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Despite their significance, comprehensive investigations of their topological characteristics and their connections to molecular interactions have eluded exploration due to experimental inaccessibility issues. This study addresses this gap by analyzing the topology of the Helmholtz energy, Gibbs energy, Grand potential, and Null potential that are associated with different isothermal boundary conditions. By employing Monte Carlo simulations in the NVT, NpT, and \u03bcVT ensembles and a molecular-based equation of state, methane, ethane, nitrogen, and methanol are investigated over a broad range of thermodynamic conditions. The predictions from the two independent methods are overall in very good agreement. Although distinct quantitative differences among the fluids are observed, the overall topology of the individual thermodynamic potentials remains unaffected by the molecular architecture, which is in line with the corresponding states principle\u2014as expected. Furthermore, a comparative analysis reveals significant differences between the total potentials and their residual contributions.<\/jats:p>","DOI":"10.1063\/5.0207592","type":"journal-article","created":{"date-parts":[[2024,6,3]],"date-time":"2024-06-03T09:40:11Z","timestamp":1717407611000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":7,"title":["Topology of thermodynamic potentials using physical models: Helmholtz, Gibbs, Grand, and Null"],"prefix":"10.1063","volume":"160","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8388-9778","authenticated-orcid":false,"given":"Isabel","family":"Nitzke","sequence":"first","affiliation":[{"name":"Thermodynamics, Technische Universit\u00e4t Berlin 1 , 10587 Berlin, Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4578-3569","authenticated-orcid":false,"given":"Simon","family":"Stephan","sequence":"additional","affiliation":[{"name":"Laboratory of Engineering Thermodynamics, RPTU Kaiserslautern 2 , 67663 Kaiserslautern, Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7947-4051","authenticated-orcid":false,"given":"Jadran","family":"Vrabec","sequence":"additional","affiliation":[{"name":"Thermodynamics, Technische Universit\u00e4t Berlin 1 , 10587 Berlin, Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2024,6,3]]},"reference":[{"key":"2024060309394186000_c1","doi-asserted-by":"crossref","first-page":"115","DOI":"10.1007\/978-3-322-84986-1_3","volume-title":"Kinetische Theorie II: Irreversible Prozesse Einf\u00fchrung und Originaltexte","year":"1970"},{"key":"2024060309394186000_c2","doi-asserted-by":"publisher","first-page":"132","DOI":"10.1002\/andp.19053220607","volume":"322","year":"1905","journal-title":"Ann. 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