QUESTDB: a database of highly-accurate excitation energies for the electronic structure community

Abstract

We describe our efforts of the past few years to create a large set of more than 500 highly-accurate vertical excitation energies of various natures ($\pi \to {\pi }^{\ast }$, $n\to {\pi }^{\ast }$, double excitation, Rydberg, singlet, doublet, triplet, etc) in small- and medium-sized molecules. These values have been obtained using an incremental strategy which consists in combining high-order coupled cluster and selected configuration interaction calculations using increasingly large diffuse basis sets in order to reach high accuracy. One of the key aspect of the so-called QUEST database of vertical excitations is that it does not rely on any experimental values, avoiding potential biases inherently linked to experiments and facilitating theoretical cross comparisons. Following this composite protocol, we have been able to produce theoretical best estimate (TBEs) with the aug-cc-pVTZ basis set for each of these transitions, as well as basis set corrected TBEs (i.e., near the complete basis set limit) for some of them. The TBEs/aug-cc-pVTZ have been employed to benchmark a large number of (lower-order) wave function methods such as CIS(D), ADC(2), CC2, STEOM-CCSD, CCSD, CCSDR(3), CCSDT-3, ADC(3), CC3, NEVPT2, and others (including spin-scaled variants). In order to gather the huge amount of data produced during the QUEST project, we have created a website [https://lcpq.github.io/QUESTDB_website] where one can easily test and compare the accuracy of a given method with respect to various variables such as the molecule size or its family, the nature of the excited states, the type of basis set, etc. We hope that the present review will provide a useful summary of our effort so far and foster new developments around excited-state methods.

44 pages, 5 figures, 4 Tables, supplementary information available at https://doi.org/10.5281/zenodo.4297012

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• The approximate Coupled-Cluster methods CC2 and CC3 in a finite magnetic field
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• Anomalous propagators and the particle-particle channel: Bethe-Salpeter equation
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• Compactification of Determinant Expansions via Transcorrelation
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• Investigating Data Hierarchies in Multifidelity Machine Learning for Excitation Energies
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• Revisiting the performance of time-dependent density functional theory for electronic excitations: Assessment of 43 popular and recently developed functionals from rungs one to four
• Performance of range-separated long-range SOPPA short-range density functional theory method for vertical excitation energies
• A Mountaineering Strategy to Excited States: Highly-Accurate Energies and Benchmarks for Bicyclic Systems
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