{"title":"基于短程和长程离子相互作用的非对称处理的体电解质自洽静电形式主义。","authors":"Sahin Buyukdagli","doi":"10.1039/D4SM01174K","DOIUrl":null,"url":null,"abstract":"<p >We predict the thermodynamic behavior of bulk electrolytes from an ionic hard-core (HC) size-augmented self-consistent formalism incorporating asymmetrically the short- and long-range ion interactions <em>via</em> their virial and cumulant treatment, respectively. The characteristic splitting length separating these two ranges is obtained from a variational equation solved together with the Schwinger–Dyson (SD) equations. <em>Via</em> comparison with simulation results from the literature, we show that the asymmetric treatment of the distinct interaction ranges significantly extends the validity regime of our previously developed purely cumulant-level Debye–Hückel (DH) theory. Namely, for monovalent solutions with typical ion sizes, the present formalism can accurately predict up to molar concentrations the liquid pressure dominated by HC interactions, the internal energies driven by charge correlations, and the local ion distributions governed by the competition between HC and electrostatic interactions. We evaluate as well the screening length of the liquid and investigate the deviations of the macromolecular interaction range from the DH length. In fair agreement with simulations and experiments, our theory is shown to reproduce the overscreening and underscreening effects occurring respectively in submolar mono- and multivalent electrolytes.</p>","PeriodicalId":103,"journal":{"name":"Soft Matter","volume":" 45","pages":" 9104-9116"},"PeriodicalIF":2.9000,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Self-consistent electrostatic formalism of bulk electrolytes based on the asymmetric treatment of the short- and long-range ion interactions†\",\"authors\":\"Sahin Buyukdagli\",\"doi\":\"10.1039/D4SM01174K\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >We predict the thermodynamic behavior of bulk electrolytes from an ionic hard-core (HC) size-augmented self-consistent formalism incorporating asymmetrically the short- and long-range ion interactions <em>via</em> their virial and cumulant treatment, respectively. The characteristic splitting length separating these two ranges is obtained from a variational equation solved together with the Schwinger–Dyson (SD) equations. <em>Via</em> comparison with simulation results from the literature, we show that the asymmetric treatment of the distinct interaction ranges significantly extends the validity regime of our previously developed purely cumulant-level Debye–Hückel (DH) theory. Namely, for monovalent solutions with typical ion sizes, the present formalism can accurately predict up to molar concentrations the liquid pressure dominated by HC interactions, the internal energies driven by charge correlations, and the local ion distributions governed by the competition between HC and electrostatic interactions. We evaluate as well the screening length of the liquid and investigate the deviations of the macromolecular interaction range from the DH length. In fair agreement with simulations and experiments, our theory is shown to reproduce the overscreening and underscreening effects occurring respectively in submolar mono- and multivalent electrolytes.</p>\",\"PeriodicalId\":103,\"journal\":{\"name\":\"Soft Matter\",\"volume\":\" 45\",\"pages\":\" 9104-9116\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-11-06\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Soft Matter\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/sm/d4sm01174k\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Soft Matter","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/sm/d4sm01174k","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
我们通过离子硬核(HC)尺寸增强自洽形式主义预测了块状电解质的热力学行为,该形式主义通过对短程和长程离子相互作用的病毒式和累积式处理,分别非对称地纳入了短程和长程离子相互作用。通过与施文格-戴森(Schwinger-Dyson,SD)方程一起求解的变分方程,可以得到分隔这两个范围的特征分裂长度。通过与文献中的模拟结果进行比较,我们发现对不同相互作用范围的非对称处理极大地扩展了我们之前开发的纯累积级德拜-胡克尔(DH)理论的有效性机制。也就是说,对于具有典型离子尺寸的一价溶液,目前的形式主义可以准确预测由 HC 相互作用主导的液体压力、由电荷相关性驱动的内部能量以及由 HC 和静电相互作用之间的竞争所支配的局部离子分布(最高可达摩尔浓度)。我们还评估了液体的筛选长度,并研究了大分子相互作用范围与 DH 长度的偏差。与模拟和实验结果相当吻合的是,我们的理论重现了亚摩尔一价和多价电解质中分别出现的过屏蔽和欠屏蔽效应。
Self-consistent electrostatic formalism of bulk electrolytes based on the asymmetric treatment of the short- and long-range ion interactions†
We predict the thermodynamic behavior of bulk electrolytes from an ionic hard-core (HC) size-augmented self-consistent formalism incorporating asymmetrically the short- and long-range ion interactions via their virial and cumulant treatment, respectively. The characteristic splitting length separating these two ranges is obtained from a variational equation solved together with the Schwinger–Dyson (SD) equations. Via comparison with simulation results from the literature, we show that the asymmetric treatment of the distinct interaction ranges significantly extends the validity regime of our previously developed purely cumulant-level Debye–Hückel (DH) theory. Namely, for monovalent solutions with typical ion sizes, the present formalism can accurately predict up to molar concentrations the liquid pressure dominated by HC interactions, the internal energies driven by charge correlations, and the local ion distributions governed by the competition between HC and electrostatic interactions. We evaluate as well the screening length of the liquid and investigate the deviations of the macromolecular interaction range from the DH length. In fair agreement with simulations and experiments, our theory is shown to reproduce the overscreening and underscreening effects occurring respectively in submolar mono- and multivalent electrolytes.
期刊介绍:
Soft Matter is an international journal published by the Royal Society of Chemistry using Engineering-Materials Science: A Synthesis as its research focus. It publishes original research articles, review articles, and synthesis articles related to this field, reporting the latest discoveries in the relevant theoretical, practical, and applied disciplines in a timely manner, and aims to promote the rapid exchange of scientific information in this subject area. The journal is an open access journal. The journal is an open access journal and has not been placed on the alert list in the last three years.