QUEST Database of Highly-Accurate Excitation Energies

We report theoretical best estimates of vertical transition
energies
(VTEs) for a large number of excited states and molecules: the quest database. This database includes 1489 aug-cc-pVTZ VTEs
(731 singlets, 233 doublets, 461 triplets, and 64 quartets) for both
valence and Rydberg transitions occurring in molecules containing
from 1 to 16 non-hydrogen atoms. Quest also includes a significant
list of VTEs for states characterized by a partial or genuine double-excitation
character, known to be particularly challenging for many computational
methods. The vast majority of the reported values are deemed chemically
accurate, that is, are within ±0.05 eV of the FCI/aug-cc-pVTZ
estimate. This allows for a balanced assessment of the performance
of popular excited-state methodologies. We report the results of such
benchmarks for various single- and multireference wave function approaches,
and provide extensive Supporting Information allowing testing of other
models. All corresponding data associated with the quest database,
along with analysis tools, can be found in the associated GitHub repository at the following URL: https://github.com/pfloos/QUESTDB.

本研究报道了针对大量激发态与分子的垂直跃迁能（Vertical Transition Energies, VTEs）的理论最优估计值，相关数据集即为QUEST数据库。该数据库包含1489组aug-cc-pVTZ基组水平下的垂直跃迁能数据，涵盖731个单重态、233个二重态、461个三重态以及64个四重态，对应含1至16个非氢原子的分子中的价态跃迁与里德堡（Rydberg）跃迁。QUEST数据库还收录了大量具有部分或真实双激发特征的态的垂直跃迁能数据，这类态被公认为诸多计算方法的挑战性测试对象。本研究报道的绝大多数数据均达到化学精度，即与全构型相互作用（Full Configuration Interaction, FCI）/aug-cc-pVTZ估计值的偏差不超过±0.05 eV。这一特性使得该数据库能够对主流激发态计算方法的性能开展均衡评估。本研究同时报道了针对各类单参考与多参考波函数方法的基准测试结果，并提供了丰富的补充材料以供其他模型的测试验证。QUEST数据库的全部关联数据与分析工具均可在以下链接对应的GitHub仓库中获取：https://github.com/pfloos/QUESTDB。