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Excitation Energies from the Entanglement Coupled Cluster Model for Doublets
Sarai Dery Folkestad1, Kristine Lauvstad Kruken1, Henrik Koch1
1Department of Chemistry, Norwegian University of Science and Technology, NTNU, Trondheim 7491, Norway.
Abstract:
We present a spin-adapted coupled cluster singles and doubles model for the excitation energies of molecular doublets. 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 are retained: an unambiguous definition of the cluster operator and a terminating Baker-Campbell-Hausdorff expansion. The model produces excitation energies of a quality comparable to that of 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.
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