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State-Specific Configuration Interaction for Excited States

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Abstract

We introduce and benchmark a new systematically improvable route for excited-state calculations, state-specific configuration interaction ($\Delta$CI). Starting with a reference built from optimized configuration state functions, separate CI calculations are performed for each targeted state (hence state-specific orbitals and determinants). Accounting for single and double excitations produces the $\Delta$CISD model, which can be improved with second-order Epstein-Nesbet perturbation theory ($\Delta$CISD+EN2) or a posteriori Davidson corrections ($\Delta$CISD+Q). These models were gauged against a vast and diverse set of 294 reference excitation energies. We have found that $\Delta$CI is significantly more accurate than standard ground-state-based CI, whereas close performances were found between $\Delta$CISD and EOM-CC2, and between $\Delta$CISD+EN2 and EOM-CCSD. For larger systems, $\Delta$CISD+Q delivers more accurate results than EOM-CC2 and EOM-CCSD. The $\Delta$CI route can handle challenging multireference problems, singly- and doubly-excited states, from closed- and open-shell species, with overall comparable accuracy, and thus represents a promising alternative to more established methodologies.
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hal-03843259 , version 1 (09-11-2022)

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Fábris Kossoski, Pierre-François Loos. State-Specific Configuration Interaction for Excited States. 2022. ⟨hal-03843259⟩
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