Monash Computational Chemistry Group, School of Chemistry, Monash University , 17 Rainforest Walk, Clayton, Victoria 3800, Australia.
Chem Rev. 2017 May 24;117(10):6696-6754. doi: 10.1021/acs.chemrev.6b00528. Epub 2017 Jan 31.
The accurate prediction of physicochemical properties of condensed systems is a longstanding goal of theoretical (quantum) chemistry. Ionic liquids comprising entirely of ions provide a unique challenge in this respect due to the diverse chemical nature of available ions and the complex interplay of intermolecular interactions among them, thus resulting in the wide variability of physicochemical properties, such as thermodynamic, transport, and spectroscopic properties. It is well understood that intermolecular forces are directly linked to physicochemical properties of condensed systems, and therefore, an understanding of this relationship would greatly aid in the design and synthesis of functionalized materials with tailored properties for an application at hand. This review aims to give an overview of how electronic structure properties obtained from quantum chemical methods such as interaction/binding energy and its fundamental components, dipole moment, polarizability, and orbital energies, can help shed light on the energetic, physical, and spectroscopic properties of semi-Coulomb systems such as ionic liquids. Particular emphasis is given to the prediction of their thermodynamic, transport, spectroscopic, and solubilizing properties.
准确预测凝聚态系统的物理化学性质是理论（量子）化学的长期目标。由于可用离子的化学性质多种多样，以及它们之间的分子间相互作用复杂，完全由离子组成的离子液体在这方面带来了独特的挑战，从而导致物理化学性质的广泛可变性，如热力学、输运和光谱性质。人们清楚地认识到，分子间力与凝聚态系统的物理化学性质直接相关，因此，对这种关系的理解将极大地有助于设计和合成具有特定功能的材料，以满足当前应用的需要。这篇综述旨在概述如何从量子化学方法（如相互作用/结合能及其基本组成部分、偶极矩、极化率和轨道能）获得的电子结构性质，帮助阐明半库仑系统（如离子液体）的能量、物理和光谱性质。特别强调了对它们的热力学、输运、光谱和溶解性质的预测。
