论文标题
寻求高度准确的激发能量：计算观点
The Quest For Highly Accurate Excitation Energies: A Computational Perspective
论文作者
论文摘要
我们提供了连续的步骤概述，这些步骤可以使用计算化学工具获得越来越准确的激发能，最终导致化学准确的中小型分子的垂直过渡能。首先，我们描述了用于定义基准值的\ textit {ab intio}方法的演变，最初是Roos的Caspt2方法，然后是著名的Thiel集合中的CC3方法，以及最近选择的配置相互作用方法的复苏。后一种方法能够始终如一地传递单个和双重激发，高度精确的小分子的激发能，以及具有紧凑基料集的中等大小分子。其次，我们描述了这些高级方法和代表性基准的激发能量集如何允许公平，准确地评估计算较轻方法的性能。我们通过讨论该领域的未来理论和技术发展来得出结论。
We provide an overview of the successive steps that made 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 \textit{ab initio} methods employed to define benchmark values, with originally 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 to assess fairly and accurately the performance of computationally lighter methods. We conclude by discussing the future theoretical and technological developments in the field.
