{"title":"团簇热力学中的经典成核理论和托尔曼方程:它们到底有多小?","authors":"Bin Chen","doi":"10.1021/acs.jpca.5c02843","DOIUrl":null,"url":null,"abstract":"<p><p>Classical nucleation theory and the Tolman equation are two fundamental theories in cluster thermodynamics. Despite their long-standing existence, the applicability of these theories remains questionable. Direct experimental validation is challenging due to the small size of the clusters involved. While theoretical approaches are often used as alternatives, the findings are frequently controversial. In this work, free energy calculations were performed across an unprecedentedly large size range using sophisticated techniques, including aggregation-volume-bias Monte Carlo, for two systems: Lennard-Jones and TIP4<i>P</i>/2005 water. The availability of bulk-phase properties for an infinitely large system (i.e., γ<sup>∞</sup>) facilitates a direct comparison to these two theories. The simulation results provide strong support for the applicability of these theories to large clusters, down to those containing a few hundred particles. However, these theories break down for small clusters.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"6018-6023"},"PeriodicalIF":2.8000,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12257522/pdf/","citationCount":"0","resultStr":"{\"title\":\"Classical Nucleation Theory and Tolman Equation in Cluster Thermodynamics: How Small Can They Truly Apply?\",\"authors\":\"Bin Chen\",\"doi\":\"10.1021/acs.jpca.5c02843\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Classical nucleation theory and the Tolman equation are two fundamental theories in cluster thermodynamics. Despite their long-standing existence, the applicability of these theories remains questionable. Direct experimental validation is challenging due to the small size of the clusters involved. While theoretical approaches are often used as alternatives, the findings are frequently controversial. In this work, free energy calculations were performed across an unprecedentedly large size range using sophisticated techniques, including aggregation-volume-bias Monte Carlo, for two systems: Lennard-Jones and TIP4<i>P</i>/2005 water. The availability of bulk-phase properties for an infinitely large system (i.e., γ<sup>∞</sup>) facilitates a direct comparison to these two theories. The simulation results provide strong support for the applicability of these theories to large clusters, down to those containing a few hundred particles. However, these theories break down for small clusters.</p>\",\"PeriodicalId\":59,\"journal\":{\"name\":\"The Journal of Physical Chemistry A\",\"volume\":\" \",\"pages\":\"6018-6023\"},\"PeriodicalIF\":2.8000,\"publicationDate\":\"2025-07-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12257522/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry A\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.jpca.5c02843\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2025/6/27 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpca.5c02843","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/6/27 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Classical Nucleation Theory and Tolman Equation in Cluster Thermodynamics: How Small Can They Truly Apply?
Classical nucleation theory and the Tolman equation are two fundamental theories in cluster thermodynamics. Despite their long-standing existence, the applicability of these theories remains questionable. Direct experimental validation is challenging due to the small size of the clusters involved. While theoretical approaches are often used as alternatives, the findings are frequently controversial. In this work, free energy calculations were performed across an unprecedentedly large size range using sophisticated techniques, including aggregation-volume-bias Monte Carlo, for two systems: Lennard-Jones and TIP4P/2005 water. The availability of bulk-phase properties for an infinitely large system (i.e., γ∞) facilitates a direct comparison to these two theories. The simulation results provide strong support for the applicability of these theories to large clusters, down to those containing a few hundred particles. However, these theories break down for small clusters.
期刊介绍:
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.