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Pré-Publication, Document De Travail Année : 2024

State-Specific Coupled-Cluster Methods for Excited States

Résumé

We reexamine ∆CCSD, a state-specific coupled-cluster (CC) with single and double excitations (CCSD) approach that targets excited states through the utilization of non-Aufbau determinants. This methodology is particularly efficient when dealing with doubly excited states, a domain where the standard equation-of-motion CCSD (EOM-CCSD) formalism falls short. Our goal here is to evaluate the effectiveness of ∆CCSD when applied to other types of excited states, comparing its consistency and accuracy with EOM-CCSD. To this end, we report a benchmark on excitation energies computed with the ∆CCSD and EOM-CCSD methods, for a set of molecular excited-state energies that encompasses not only doubly excited states but also doublet-doublet transitions and (singlet and triplet) singly-excited states of closed-shell systems. In the latter case, we rely on a minimalist version of multireference CC known as the two-determinant CCSD method to compute the excited states. Our dataset, consisting of 276 excited states stemming from the quest database [Véril et al., WIREs Comput. Mol. Sci. 2021, 11, e1517], provides a significant base to draw general conclusions concerning the accuracy of ∆CCSD. Except for the doubly-excited states, we found that ∆CCSD underperforms EOM-CCSD. For doublet-doublet transitions, the difference between the mean absolute errors (MAEs) of the two methodologies (of 0.10 eV and 0.07 eV) is less pronounced than that obtained for singly-excited states of closed-shell systems (MAEs of 0.15 eV and 0.08 eV). This discrepancy is largely attributed to a greater number of excited states in the latter set exhibiting multiconfigurational characters, which are more challenging for ∆CCSD. We also found typically small improvements by employing state-specific optimized orbitals.
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Dates et versions

hal-04387158 , version 1 (11-01-2024)

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Yann Damour, Anthony Scemama, Denis Jacquemin, Fábris Kossoski, Pierre-Francois Loos. State-Specific Coupled-Cluster Methods for Excited States. 2024. ⟨hal-04387158⟩
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