The Quest for Highly Accurate Excitation Energies: A Computational Perspective
The Quest for Highly Accurate Excitation Energies: A Computational Perspective
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DOI：
10.1021/acs.jpclett.0c00014
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发表时间：
2020-03-19
影响因子：
5.7
通讯作者：
Jacquemin, Denis
中科院分区：
文献类型：
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作者：
Loos, Pierre-Francois;Scemama, Anthony;Jacquemin, Denis
我们概述了连续的步骤，这些步骤使得使用计算化学工具获得越来越精确的激发能成为可能，最终导致化学精确的中小分子垂直转变能量。首先，我们描述了用于定义基准值的从头算方法的演变，包括最初的Roos CASPT2方法，然后是著名的Thiel集合中的CC3方法，以及最近重新兴起的选定配置交互方法。后一种方法能够为小分子和具有紧凑基集的中等大小分子提供一致的单激发和双激发，高度精确的激发能。其次，我们描述了这些高级方法和具有代表性的激发能基准集的创建如何允许公平和准确地评估计算较轻的方法的性能。最后，我们讨论了该领域未来可能的理论和技术发展。
We provide an overview of the successive steps that made it possible to obtain increasingly accurate excitation energies with computational chemistry tools, eventually leading to chemically accurate vertical transition energies for small- and medium-size molecules. First, we describe the evolution of ab initio methods employed to define benchmark values, with the original Roos CASPT2 method, then the CC3 method as in the renowned Thiel set, and more recently the resurgence of selected configuration interaction methods. The latter method has been able to deliver consistently, for both single and double excitations, highly accurate excitation energies for small molecules, as well as medium-size molecules with compact basis sets. Second, we describe how these high-level methods and the creation of representative benchmark sets of excitation energies have allowed the fair and accurate assessment of the performance of computationally lighter methods. We conclude by discussing possible future theoretical and technological developments in the field.