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Auteurs principaux: Folkestad, Sarai Dery, Kruken, Kristine Lauvstad, Koch, Henrik
Format: Preprint
Publié: 2025
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Accès en ligne:https://arxiv.org/abs/2504.04459
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author Folkestad, Sarai Dery
Kruken, Kristine Lauvstad
Koch, Henrik
author_facet Folkestad, Sarai Dery
Kruken, Kristine Lauvstad
Koch, Henrik
contents We present excitation energies for molecular doublets from a spin-adapted formulation of coupled cluster singles and doubles theory. The entanglement coupled cluster approach represents an unconventional take on the notorious problem of spin adaptation for open-shell species. In this approach, the high-spin open-shell molecular system is coupled to non-interacting bath orbitals to form a total closed-shell system. In entanglement coupled cluster theory, many of the attractive features of the spin-adapted closed-shell coupled cluster is retained: an unambiguous definition of the cluster operator and a terminating Baker-Campbell-Hausdorff expansion. The result is a spin-adapted coupled cluster theory for open-shell species. The model produces excitation energies of a quality comparable to the closed-shell counterpart. Additionally, some ionized states that cannot be modeled accurately with the alternative equation-of-motion approach for ionized states, can be described with the entanglement coupled cluster singles and doubles model.
format Preprint
id arxiv_https___arxiv_org_abs_2504_04459
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Excitation Energies from the Entanglement Coupled Cluster Model for Doublets
Folkestad, Sarai Dery
Kruken, Kristine Lauvstad
Koch, Henrik
Chemical Physics
We present excitation energies for molecular doublets from a spin-adapted formulation of coupled cluster singles and doubles theory. The entanglement coupled cluster approach represents an unconventional take on the notorious problem of spin adaptation for open-shell species. In this approach, the high-spin open-shell molecular system is coupled to non-interacting bath orbitals to form a total closed-shell system. In entanglement coupled cluster theory, many of the attractive features of the spin-adapted closed-shell coupled cluster is retained: an unambiguous definition of the cluster operator and a terminating Baker-Campbell-Hausdorff expansion. The result is a spin-adapted coupled cluster theory for open-shell species. The model produces excitation energies of a quality comparable to the closed-shell counterpart. Additionally, some ionized states that cannot be modeled accurately with the alternative equation-of-motion approach for ionized states, can be described with the entanglement coupled cluster singles and doubles model.
title Excitation Energies from the Entanglement Coupled Cluster Model for Doublets
topic Chemical Physics
url https://arxiv.org/abs/2504.04459