{"title":"离子液体混合物中的波动力学","authors":"Timothy S. Groves and Susan Perkin","doi":"10.1039/D4FD00040D","DOIUrl":null,"url":null,"abstract":"<p >Experimental measurements of interactions in ionic liquids and concentrated electrolytes over the past decade or so have revealed simultaneous monotonic and oscillatory decay modes. These observations have been hard to interpret using classical theories, which typically allow for just one electrostatic decay mode in electrolytes. Meanwhile, substantial progress in the theoretical description of dielectric response and ion correlations in electrolytes has illuminated the deep connection between density and charge correlations and the multiplicity of decay modes characterising a liquid electrolyte. The challenge in front of us is to build connections between the theoretical expressions for a pair of correlation functions and the directly measured free energy of interaction between macroscopic surfaces in experiments. Towards this aim, we here present measurements and analysis of the interactions between macroscopic bodies across a fluid mixture of two ionic liquids of widely diverging ionic size. The measured oscillatory interaction forces in the liquid mixtures are significantly more complex than for either of the pure ionic liquids, but can be fitted to a superposition of two oscillatory and one monotonic mode with parameters matching those of the pure liquids. We discuss this empirical finding, which hints at a kind of wave mechanics for interactions in liquid matter.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"253 ","pages":" 193-211"},"PeriodicalIF":3.4000,"publicationDate":"2024-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/fd/d4fd00040d?page=search","citationCount":"0","resultStr":"{\"title\":\"Wave mechanics in an ionic liquid mixture\",\"authors\":\"Timothy S. Groves and Susan Perkin\",\"doi\":\"10.1039/D4FD00040D\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Experimental measurements of interactions in ionic liquids and concentrated electrolytes over the past decade or so have revealed simultaneous monotonic and oscillatory decay modes. These observations have been hard to interpret using classical theories, which typically allow for just one electrostatic decay mode in electrolytes. Meanwhile, substantial progress in the theoretical description of dielectric response and ion correlations in electrolytes has illuminated the deep connection between density and charge correlations and the multiplicity of decay modes characterising a liquid electrolyte. The challenge in front of us is to build connections between the theoretical expressions for a pair of correlation functions and the directly measured free energy of interaction between macroscopic surfaces in experiments. Towards this aim, we here present measurements and analysis of the interactions between macroscopic bodies across a fluid mixture of two ionic liquids of widely diverging ionic size. The measured oscillatory interaction forces in the liquid mixtures are significantly more complex than for either of the pure ionic liquids, but can be fitted to a superposition of two oscillatory and one monotonic mode with parameters matching those of the pure liquids. We discuss this empirical finding, which hints at a kind of wave mechanics for interactions in liquid matter.</p>\",\"PeriodicalId\":49075,\"journal\":{\"name\":\"Faraday Discussions\",\"volume\":\"253 \",\"pages\":\" 193-211\"},\"PeriodicalIF\":3.4000,\"publicationDate\":\"2024-03-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2024/fd/d4fd00040d?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Faraday Discussions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/fd/d4fd00040d\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"Chemistry\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Faraday Discussions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/fd/d4fd00040d","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"Chemistry","Score":null,"Total":0}
Experimental measurements of interactions in ionic liquids and concentrated electrolytes over the past decade or so have revealed simultaneous monotonic and oscillatory decay modes. These observations have been hard to interpret using classical theories, which typically allow for just one electrostatic decay mode in electrolytes. Meanwhile, substantial progress in the theoretical description of dielectric response and ion correlations in electrolytes has illuminated the deep connection between density and charge correlations and the multiplicity of decay modes characterising a liquid electrolyte. The challenge in front of us is to build connections between the theoretical expressions for a pair of correlation functions and the directly measured free energy of interaction between macroscopic surfaces in experiments. Towards this aim, we here present measurements and analysis of the interactions between macroscopic bodies across a fluid mixture of two ionic liquids of widely diverging ionic size. The measured oscillatory interaction forces in the liquid mixtures are significantly more complex than for either of the pure ionic liquids, but can be fitted to a superposition of two oscillatory and one monotonic mode with parameters matching those of the pure liquids. We discuss this empirical finding, which hints at a kind of wave mechanics for interactions in liquid matter.