State-Specific Configuration Interaction for Excited States - Fédération de recherche « Matière et interactions » Accéder directement au contenu
Article Dans Une Revue Journal of Chemical Theory and Computation Année : 2023

State-Specific Configuration Interaction for Excited States

Fábris Kossoski
Pierre-François Loos

Résumé

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.
Fichier principal
Vignette du fichier
2211.03048.pdf (329.11 Ko) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-03843259 , version 1 (09-11-2022)

Identifiants

Citer

Fábris Kossoski, Pierre-François Loos. State-Specific Configuration Interaction for Excited States. Journal of Chemical Theory and Computation, 2023, 19 (8), pp.2258-2269. ⟨10.1021/acs.jctc.3c00057⟩. ⟨hal-03843259⟩
61 Consultations
111 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More