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000005355 005__ 20251007025230.0
000005355 02470 $$ahttps://doi.org/10.1021/acs.jctc.2c00630$$2doi
000005355 037__ $$aTEXTUAL$$bArticle
000005355 041__ $$aeng
000005355 245__ $$aLarge-Scale Benchmarking of Multireference Vertical-Excitation Calculations via Automated Active-Space Selection
000005355 269__ $$a2022-09-16
000005355 336__ $$aArticle
000005355 520__ $$aWe have calculated state-averaged complete-active-space self-consistent-field (SA-CASSCF), multiconfiguration pair-density functional theory (MC-PDFT), hybrid MC-PDFT (HMC-PDFT), and n-electron valence state second-order perturbation theory (NEVPT2) excitation energies with the approximate pair coefficient (APC) automated active-space selection scheme for the QUESTDB benchmark database of 542 vertical excitation energies. We eliminated poor active spaces (20–40% of calculations) by applying a threshold to the SA-CASSCF absolute error. With the remaining calculations, we find that NEVPT2 performance is significantly impacted by the size of the basis set the wave functions are converged in, regardless of the quality of their description, which is a problem absent in MC-PDFT. Additionally, we find that HMC-PDFT is a significant improvement over MC-PDFT with the translated PBE (tPBE) density functional and that it performs about as well as NEVPT2 and second-order coupled cluster on a set of 373 excitations in the QUESTDB database. We optimized the percentage of SA-CASSCF energy to include in HMC-PDFT when using the tPBE on-top functional, and we find the 25% value used in tPBE0 to be optimal. This work is by far the largest benchmarking of MC-PDFT and HMC-PDFT to date, and the data produced in this work are useful as a validation of HMC-PDFT and of the APC active-space selection scheme. We have made all the wave functions produced in this work (orbitals and CI vectors) available to the public and encourage the community to utilize this data as a tool in the development of further multireference model chemistries.
000005355 536__ $$oNational Science Foundation$$cCHE-2054723
000005355 540__ $$a&lt;p&gt;© 2022 The Authors&lt;/p&gt; &lt;p&gt;This work is licensed under the &lt;a href="http://creativecommons.org/licenses/by/4.0/" target="_blank"&gt;Creative Commons Attribution License&lt;/a&gt;.&lt;/p&gt;
000005355 542__ $$fCC BY
000005355 594__ $$aWe have made available all the data necessary to reproduce and explore our results (orbitals, CI vectors, and metadata for all 3237 converged SA-CASSCF calculations) via Zenodo: &lt;a href="https://doi.org/10.5281/zenodo.6644169" target="_blank"&gt;https://doi.org/10.5281/zenodo.6644169&lt;/a&gt;
000005355 690__ $$aPhysical Sciences Division
000005355 690__ $$aPritzker School of Molecular Engineering
000005355 691__ $$aChemistry
000005355 692__ $$aChicago Center for Theoretical Chemistry
000005355 692__ $$aJames Franck Institute
000005355 7001_ $$1https://orcid.org/0000-0003-0208-5274$$2ORCID$$aKing, Daniel S.$$uUniversity of Chicago
000005355 7001_ $$1https://orcid.org/0000-0001-7807-2950$$2ORCID$$aHermes, Matthew R.$$uUniversity of Chicago
000005355 7001_ $$1https://orcid.org/0000-0002-7742-7294$$2ORCID$$aTruhlar, Donald G.$$uUniversity of Minnesota
000005355 7001_ $$1https://orcid.org/0000-0001-5227-1396$$2ORCID$$aGagliardi, Laura$$uUniversity of Chicago
000005355 773__ $$tJournal of Chemical Theory and Computation
000005355 8564_ $$yArticle$$920de1399-a822-47b5-8132-b78f930a946f$$s2823896$$uhttps://knowledge.uchicago.edu/record/5355/files/Large-Scale-Benchmarking-of-Multireference-Vertical-Excitation-Calculations-via-Automated-Active-Space-Selection.pdf$$ePublic
000005355 8564_ $$ySupporting information$$952ca2153-83cb-4be4-953a-d1de97dee230$$s10162696$$uhttps://knowledge.uchicago.edu/record/5355/files/ct2c00630_si_001.pdf$$ePublic
000005355 908__ $$aI agree
000005355 909CO $$ooai:uchicago.tind.io:5355$$pGLOBAL_SET
000005355 983__ $$aArticle