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.
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7 July 2020
Research Article|
July 07 2020
Analytic gradients for state-averaged multiconfiguration pair-density functional theory
Thais R. Scott
;
Thais R. Scott
1
Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota
, Minneapolis, Minnesota 55455, USA
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Matthew R. Hermes;
Matthew R. Hermes
1
Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota
, Minneapolis, Minnesota 55455, USA
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Andrew M. Sand
;
Andrew M. Sand
2
Department of Chemistry and Biochemistry, Butler University
, Indianapolis, Indiana 46208, USA
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Meagan S. Oakley
;
Meagan S. Oakley
1
Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota
, Minneapolis, Minnesota 55455, USA
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Donald G. Truhlar
;
Donald G. Truhlar
a)
1
Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota
, Minneapolis, Minnesota 55455, USA
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Laura Gagliardi
Laura Gagliardi
a)
1
Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota
, Minneapolis, Minnesota 55455, USA
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Thais R. Scott
1
Matthew R. Hermes
1
Andrew M. Sand
2
Meagan S. Oakley
1
Donald G. Truhlar
1,a)
Laura Gagliardi
1,a)
1
Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota
, Minneapolis, Minnesota 55455, USA
2
Department of Chemistry and Biochemistry, Butler University
, Indianapolis, Indiana 46208, USA
J. Chem. Phys. 153, 014106 (2020)
Article history
Received:
March 09 2020
Accepted:
May 28 2020
Citation
Thais R. Scott, Matthew R. Hermes, Andrew M. Sand, Meagan S. Oakley, Donald G. Truhlar, Laura Gagliardi; Analytic gradients for state-averaged multiconfiguration pair-density functional theory. J. Chem. Phys. 7 July 2020; 153 (1): 014106. https://doi.org/10.1063/5.0007040
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