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arXiv · 1911.01570

Capturing Multireference Excited States by Constrained DFT

Nell Karpinski·Pablo Ramos·Michele Pavanello
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Abstract

The computation of excited electronic states with commonly employed (approximate) methods is challenging, typically yielding states of lower quality than the corresponding ground state for a higher computational cost. In this work, we present a mean field method that extends the previously proposed eXcited Constrained DFT (XCDFT) from single Slater determinants to ensemble 1-RDMs for computing low-lying excited states. The method still retains an associated computational complexity comparable to a semilocal DFT calculation while at the same time is capable of approaching states with multireference character. We benchmark the quality of this method on well-established test sets, finding good descriptions of the electronic structure of multireference states and maintaining an overall accuracy for the predicted excitation energies comparable to semilocal TDDFT.

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Nell Karpinski, Pablo Ramos, Michele Pavanello. 2019-11-05. Capturing Multireference Excited States by Constrained DFT. https://doi.org/10.1103/physreva.101.032510

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