CL&P: A generic and systematic force field for ionic liquids modeling

摘要

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.