Quantitative Equivalence and Performance Comparison of Particle and Field-Theoretic Simulations

IF 5.1 1区 化学 Q1 POLYMER SCIENCE Macromolecules Pub Date : 2024-11-12 DOI:10.1021/acs.macromol.4c02034
Joshua Lequieu
{"title":"Quantitative Equivalence and Performance Comparison of Particle and Field-Theoretic Simulations","authors":"Joshua Lequieu","doi":"10.1021/acs.macromol.4c02034","DOIUrl":null,"url":null,"abstract":"Particle and field-theoretic simulations are both commonly used methods to study the equilibrium properties of polymeric materials. Yet despite the formal equivalence of the two methods, no comprehensive comparisons of particle and field-theoretic simulations exist in the literature. In this work, we seek to fill this gap by performing a systematic and quantitative comparison of particle and field-theoretic simulations. In our comparison, we consider four representative polymeric systems: a homopolymer melt/solution, a diblock copolymer melt, a polyampholyte solution, and a polyelectrolyte gel. For each of these systems, we first demonstrate that particle and field-theoretic simulations are equivalent and yield exactly the same results for the pressure and the chemical potential. We next quantify the performance of each method across a range of different conditions including variations in chain length, system density, interaction strength, system size, and polymer volume fraction. The outcome of these calculations is a comprehensive look into the performance of each method and the systems and conditions when either particle or field-theoretic simulations are preferred. We find that field-theoretic simulations are equal to or faster than particle simulations for nearly all of the systems and conditions examined. In many situations, field-theoretic simulations are several orders of magnitude faster than particle simulations, especially if the polymer chains are long, the system density is high, and long-range Coulombic interactions are present. We also demonstrate that field-theoretic simulations are considerably faster at calculating the chemical potential and bypass the challenges associated with particle-based Widom insertion techniques. Taken together, our results provide quantitative evidence that field-theoretic simulations can reach and sample equilibrium considerably faster than particle simulations while simultaneously producing equivalent results.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":null,"pages":null},"PeriodicalIF":5.1000,"publicationDate":"2024-11-12","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.4c02034","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
引用次数: 0

Abstract

Particle and field-theoretic simulations are both commonly used methods to study the equilibrium properties of polymeric materials. Yet despite the formal equivalence of the two methods, no comprehensive comparisons of particle and field-theoretic simulations exist in the literature. In this work, we seek to fill this gap by performing a systematic and quantitative comparison of particle and field-theoretic simulations. In our comparison, we consider four representative polymeric systems: a homopolymer melt/solution, a diblock copolymer melt, a polyampholyte solution, and a polyelectrolyte gel. For each of these systems, we first demonstrate that particle and field-theoretic simulations are equivalent and yield exactly the same results for the pressure and the chemical potential. We next quantify the performance of each method across a range of different conditions including variations in chain length, system density, interaction strength, system size, and polymer volume fraction. The outcome of these calculations is a comprehensive look into the performance of each method and the systems and conditions when either particle or field-theoretic simulations are preferred. We find that field-theoretic simulations are equal to or faster than particle simulations for nearly all of the systems and conditions examined. In many situations, field-theoretic simulations are several orders of magnitude faster than particle simulations, especially if the polymer chains are long, the system density is high, and long-range Coulombic interactions are present. We also demonstrate that field-theoretic simulations are considerably faster at calculating the chemical potential and bypass the challenges associated with particle-based Widom insertion techniques. Taken together, our results provide quantitative evidence that field-theoretic simulations can reach and sample equilibrium considerably faster than particle simulations while simultaneously producing equivalent results.

Abstract Image

查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
粒子模拟与场论模拟的定量等效性和性能比较
粒子模拟和场论模拟都是研究聚合物材料平衡特性的常用方法。然而,尽管这两种方法在形式上等同,但文献中并没有对粒子模拟和场论模拟进行全面的比较。在这项工作中,我们试图通过对粒子模拟和场论模拟进行系统的定量比较来填补这一空白。在比较中,我们考虑了四个具有代表性的聚合物系统:均聚物熔体/溶液、二嵌段共聚物熔体、聚酰胺溶液和聚电解质凝胶。对于其中的每一种体系,我们首先证明粒子模拟和场论模拟是等效的,并且在压力和化学势方面得到的结果完全相同。接下来,我们量化了每种方法在一系列不同条件下的性能,包括链长、系统密度、相互作用强度、系统尺寸和聚合物体积分数的变化。这些计算的结果全面考察了每种方法的性能,以及粒子模拟或场理论模拟更受青睐的系统和条件。我们发现,在几乎所有考察过的系统和条件下,场理论模拟都等同于或快于粒子模拟。在许多情况下,场理论模拟比粒子模拟快几个数量级,尤其是在聚合物链长、系统密度高以及存在长程库仑相互作用的情况下。我们还证明,场理论模拟在计算化学势方面要快得多,而且可以绕过与基于粒子的 Widom 插入技术相关的挑战。总之,我们的研究结果提供了定量证据,证明场理论模拟能比粒子模拟更快地达到平衡并对平衡进行采样,同时产生等效的结果。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 去求助
来源期刊
Macromolecules
Macromolecules 工程技术-高分子科学
CiteScore
9.30
自引率
16.40%
发文量
942
审稿时长
2 months
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.
期刊最新文献
Molecular-Scale Investigation of the Microphase-Dependent Load Transfer Capability of Polyurethane Synthesis and Characterization of n-Doped Poly(benzodifurandione) (n-PBDF) Derivatives via Aromatic Substitution Glyoxal-Based Bi-Oxazine Benzoxazines: Formaldehyde-Free Biothermosets Quantitative Equivalence and Performance Comparison of Particle and Field-Theoretic Simulations Renewable Furfural-Based Sulfur-Bridged Epoxy Resins with Excellent Adhesive Properties
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1