用理论工具评估0-0能量：简短回顾
Evaluating 0-0 Energies with Theoretical Tools: a Short Review
摘要：
对于给定的电子激发态，0-0能量（$T_0$或$T_{00}$）是最简单的性质，允许在理论和（准确的）实验之间进行直接和物理上合理的比较。然而，用\emph{ab initio}方法计算0-0能量需要确定激发态的结构和振动频率，这限制了在实践中可以考虑的理论模型的质量。这就解释了为什么只有相当有限的，但不断增加的工作数量已致力于确定这一属性。在这方面的贡献，我们审查这些努力，重点是基准研究进行气相和溶剂化化合物。多年来，不仅随着分子尺寸的增加，而且理论工具的改进也遵循了同样的趋势。虽然在这些基准中获得的结果显著地取决于协议的细节和激发态的性质，但是在价态跃迁的情况下，现在可以粗略地估计理论方案的总体精度如下：当使用杂化泛函时，CIS的$1$ eV，CIS（D）的$0.2$- $0.3$ eV，TD-DFT的$0.2$- $0.4$ eV，$0.1$ --ADC（2）和CC 2的$0.2$ eV，以及CC 3的$0.04$ eV，后一种方法是唯一一种在接近系统的基础上提供化学准确度的方法。
英文摘要：
For a given electronic excited state, the 0-0 energy ($T_0$ or $T_{00}$) is the simplest property allowing straightforward and physically-sound comparisons between theory and (accurate) experiment. However, the computation of 0-0 energies with \emph{ab initio} approaches requires determining both the structure and the vibrational frequencies of the excited state, which limits the quality of the theoretical models that can be considered in practice. This explains why only a rather limited, yet constantly increasing, number of works have been devoted to the determination of this property. In this contribution, we review these efforts with a focus on benchmark studies carried out for both gas phase and solvated compounds. Over the years, not only as the size of the molecules increased, but the refinement of the theoretical tools has followed the same trend. Though the results obtained in these benchmarks significantly depend on both the details of the protocol and the nature of the excited states, one can now roughly estimate, in the case of valence transitions, the overall accuracy of theoretical schemes as follows: $1$ eV for CIS, $0.2$--$0.3$ eV for CIS(D), $0.2$--$0.4$ eV for TD-DFT when one employs hybrid functionals, $0.1$--$0.2$ eV for ADC(2) and CC2, and $0.04$ eV for CC3, the latter approach being the only one delivering chemical accuracy on a near-systematic basis.
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