{"title":"在聚合物电解质的一般粗粒度分子动力学模拟中,使用德鲁德振荡器捕获离子溶剂化","authors":"Mengdi Fan, Lisa M. Hall","doi":"10.1021/acs.macromol.4c02082","DOIUrl":null,"url":null,"abstract":"Generic bead–spring models with Lennard–Jones interactions are commonly used to study uncharged polymeric materials. However, incorporating ions into polymer systems requires additional model features to address their long-ranged Coulomb interactions and their interactions with polarizable polymers. This study integrates the Drude oscillator model into coarse-grained molecular dynamics simulations to capture features of ion solvation in polymers. Specifically, we treat coarse-grained beads as polarizable entities with internal dipoles; each bead contains a Drude core bonded with a stiff spring to an oppositely charged Drude particle that does not leave the Lennard−Jones diameter of the core. We first demonstrate the feasibility of this approach in simulations of neat polymers, exploring dielectric constants ranging from 2 to 12. To manage strong local interactions in high-polarizability systems with ions, we propose combining this approach with implicit strategies such as adjusting the background dielectric constant and scaling down ion charges. By combining these explicit and implicit methods, we can gain control over structural features like ion clustering and peak heights in radial distribution functions, enhancing our ability to model features of ion solvation and dielectric response in polymer systems.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"103 1","pages":""},"PeriodicalIF":5.1000,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Using Drude Oscillators to Capture Ion Solvation in Generic Coarse-Grained Molecular Dynamics Simulations of Polymer Electrolytes\",\"authors\":\"Mengdi Fan, Lisa M. Hall\",\"doi\":\"10.1021/acs.macromol.4c02082\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Generic bead–spring models with Lennard–Jones interactions are commonly used to study uncharged polymeric materials. However, incorporating ions into polymer systems requires additional model features to address their long-ranged Coulomb interactions and their interactions with polarizable polymers. This study integrates the Drude oscillator model into coarse-grained molecular dynamics simulations to capture features of ion solvation in polymers. Specifically, we treat coarse-grained beads as polarizable entities with internal dipoles; each bead contains a Drude core bonded with a stiff spring to an oppositely charged Drude particle that does not leave the Lennard−Jones diameter of the core. We first demonstrate the feasibility of this approach in simulations of neat polymers, exploring dielectric constants ranging from 2 to 12. To manage strong local interactions in high-polarizability systems with ions, we propose combining this approach with implicit strategies such as adjusting the background dielectric constant and scaling down ion charges. By combining these explicit and implicit methods, we can gain control over structural features like ion clustering and peak heights in radial distribution functions, enhancing our ability to model features of ion solvation and dielectric response in polymer systems.\",\"PeriodicalId\":51,\"journal\":{\"name\":\"Macromolecules\",\"volume\":\"103 1\",\"pages\":\"\"},\"PeriodicalIF\":5.1000,\"publicationDate\":\"2024-12-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecules\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.macromol.4c02082\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.macromol.4c02082","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Using Drude Oscillators to Capture Ion Solvation in Generic Coarse-Grained Molecular Dynamics Simulations of Polymer Electrolytes
Generic bead–spring models with Lennard–Jones interactions are commonly used to study uncharged polymeric materials. However, incorporating ions into polymer systems requires additional model features to address their long-ranged Coulomb interactions and their interactions with polarizable polymers. This study integrates the Drude oscillator model into coarse-grained molecular dynamics simulations to capture features of ion solvation in polymers. Specifically, we treat coarse-grained beads as polarizable entities with internal dipoles; each bead contains a Drude core bonded with a stiff spring to an oppositely charged Drude particle that does not leave the Lennard−Jones diameter of the core. We first demonstrate the feasibility of this approach in simulations of neat polymers, exploring dielectric constants ranging from 2 to 12. To manage strong local interactions in high-polarizability systems with ions, we propose combining this approach with implicit strategies such as adjusting the background dielectric constant and scaling down ion charges. By combining these explicit and implicit methods, we can gain control over structural features like ion clustering and peak heights in radial distribution functions, enhancing our ability to model features of ion solvation and dielectric response in polymer systems.
期刊介绍:
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.