Large-Scale Benchmarking of Multireference Vertical-Excitation Calculations via Automated Active-Space Selection

15 June 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


We have calculated state-averaged complete-active-space self-consistent-field (SA-CASSCF), multiconfiguration pair-density functional theory (MC-PDFT), hybrid MC-PDFT (HMC-PDFT), and n-electron valence state second-order perturbation theory (NEVPT2) excitation energies with the approximate pair-coefficient (APC) automated active-space selection scheme for the QUESTDB benchmark database of 542 vertical excitation energies. We eliminated poor active spaces (20-30% of calculations) by applying a threshold to the SA-CASSCF absolute error. With the remaining calculations, we find that NEVPT2 performance is significantly impacted by the size of the basis set the wave functions are converged in regardless of the quality of their description, which is a problem absent in MC-PDFT. Additionally, we find that HMC-PDFT is a significant improvement over MC-PDFT with the tPBE density functional, and that it performs about as well as NEVPT2 and second-order coupled cluster (CC2) on a set of 373 excitations in the QUESTDB database. We optimized the percentage of SA-CASSCF energy to include in HMC-PDFT when using the tPBE on-top functional, and we find the 25% value used in tPBE0 to be optimal. This work is by far the largest benchmarking of MC-PDFT and HMC-PDFT to date, and the data produced in this work is useful as a validation of HMC-PDFT and of the APC active-space selection scheme. We have made all the wave functions produced in this work (orbitals and CI vectors) available to the public and encourage the community to utilize this data as a tool in the development of further multireference model chemistries.


Active Space Selection
Excited States

Supplementary materials

Supporting Information
Figures referred to in the main text and additional data analysis.


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