论文标题
基准测试CASPT3垂直激发能
Benchmarking CASPT3 Vertical Excitation Energies
论文作者
论文摘要
基于280个参考垂直过渡能量（单元，三胞胎，Valence，Rydberg，$ n \toπ^*$，$π\toπ^*$，以及双重激发），我们从Quest Database中提取的双重激发，我们评估第三级多等法障碍理论的准确性，caspt3，Caspt3，caspt3，在Metal Inted of Solecult of Metresmult of Soled Stand中。当人们应用有争议的电离势力 - 电子附属（IPEA）偏移时，我们表明CASPT3提供的精度与二阶对方CASPT2相似，平均绝对误差为$ 0.11 $ ev。但是，正如已经报道的那样，我们还观察到，无论过渡类型和系统尺寸如何，CASPT3的准确性几乎对IPEA偏移不敏感，当IPEA转移关闭时，平均绝对误差的平均绝对误差略有减少至0.09美元。
Based on 280 reference vertical transition energies of various natures (singlet, triplet, valence, Rydberg, $n\toπ^*$, $π\toπ^*$, and double excitations) extracted from the QUEST database, we assess the accuracy of third-order multireference perturbation theory, CASPT3, in the context of molecular excited states. When one applies the disputable ionization-potential-electron-affinity (IPEA) shift, we show that CASPT3 provides a similar accuracy as its second-order counterpart, CASPT2, with the same mean absolute error of $0.11$ eV. However, as already reported, we also observe that the accuracy of CASPT3 is almost insensitive to the IPEA shift, irrespective of the transition type and system size, with a small reduction of the mean absolute error to $0.09$ eV when the IPEA shift is switched off.
