CL&P: A generic and systematic force field for ionic liquids modeling
CL&P: A generic and systematic force field for ionic liquids modeling
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DOI：
10.1007/s00214-012-1129-7
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发表时间：
2012-03-01
影响因子：
1.7
通讯作者：
Padua, Agilio A. H.
中科院分区：
文献类型：
--
作者：
Canongia Lopes, Jose N.;Padua, Agilio A. H.
在这篇文章中，我们回顾了离子液体模拟领域中最广泛使用的力场之一的发展过程，分析了它随后的扩展和替代模型，并考虑了未来的改进途径，以克服目前的局限性。这包括描述和讨论(1)Canongia Lope&Padua(CL&P)力场的类属和系统特征背后的基本原理，即它内在的内部一致性、可转移性和兼容性规范；(2)多年来一直(并将继续)被参数化的离子液体系列以及在理论和应用方面最具挑战性的系列；(3)导致每种类型的离子及其同系族正确参数化的步骤，特别强调对它们的灵活性和电荷分布的正确建模；(4)CL&P和其他力场的验证过程；(5)在通用或特定力场、粗粒或原子模型和可极化或不可极化方法之间进行选择时必须达成的妥协。将CL&P和其他力场应用于离子液体的量子力学和统计力学研究，发现和分析了离子液体的独特性质，即离子液体是纳米分离的流体，在纳米尺度上具有结构和动态的非均质性。理论化学对离子液体领域的这一成功贡献也将在接下来的讨论中起到指导作用。
In this account, we review the process that led to the development of one of the most widely used force fields in the area of ionic liquids modeling, analyze its subsequent expansions and alternative models, and consider future routes of improvement to overcome present limitations. This includes the description and discussion of (1) the rationale behind the generic and systematic character of the Canongia Lopes & Padua (CL&P) force field, namely its built-in specifications of internal consistency, transferability, and compatibility; (2) the families of ionic liquids that have been (and continue to be) parameterized over the years and those that are the most challenging both in theoretical and applied terms; (3) the steps that lead to a correct parameterization of each type of ion and its homologous family, with special emphasis on the correct modeling of their flexibility and charge distribution; (4) the validation processes of the CL&P and other force fields; and finally (5) the compromises that have to be attained when choosing between generic or specific force fields, coarse-grain or atomistic models, and polarizable or non-polarizable methods. The application of the CL&P and other force fields to the study of ionic liquids using quantum- and statistical-mechanics methods has led to the discovery and analysis of the unique nature of their liquid phases, that is, the notion that ionic liquids are nano-segregated fluids with structural and dynamic heterogeneities at the nanoscopic scale. This successful contribution of theoretical chemistry to the field of ionic liquids will also serve as a guide throughout the ensuing discussion.