Analytic gradients for state-averaged multiconfiguration pair-density functional theory

Thais Scott, Matthew R. Hermes, Andrew M. Sand, Meagan S Oakley, Donald G. Truhlar, Laura Gagliardi

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Analytic gradients are important for efficient calculations of stationary points on potential energy surfaces, for interpreting spectroscopic observations, and for efficient direct dynamics simulations. For excited electronic states, as are involved in UV-Vis spectroscopy and photochemistry, analytic gradients are readily available and often affordable for calculations using a state-averaged complete active space self-consistent-field (SA-CASSCF) wave function. However, in most cases, a post-SA-CASSCF step is necessary for quantitative accuracy, and such calculations are often too expensive if carried out by perturbation theory or configuration interaction. In this work, we present the analytic gradients for multiconfiguration pair-density functional theory based on SA-CASSCF wave functions, which is a more affordable alternative. A test set of molecules has been studied with this method, and the stationary geometries and energetics are compared to values in the literature as obtained by other methods. Excited-state geometries computed with state-averaged pair-density functional theory have similar accuracy to those from complete active space perturbation theory at the second-order.

Original languageEnglish (US)
Article number014106
JournalJournal of Chemical Physics
Issue number1
StatePublished - Jul 7 2020

Bibliographical note

Funding Information:
This work was supported by the National Science Foundation under Grant No. CHE-1764186. The authors acknowledge Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing resources that contributed to the research results reported within this paper. T.R.S. acknowledges that this material is also based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. CON-75851, Project No. 00074041. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation.

Publisher Copyright:
© 2020 Author(s).


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