Cluster perturbation theory. II. Excitation energies for a coupled cluster target state

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In cluster perturbation (CP) theory, we consider a target excitation space relative to a Hartree-Fock state and partition the target excitation space into a parent excitation space and an auxiliary excitation space. The zeroth-order state is in CP theory a coupled cluster (CC) state in the parent excitation space, and the target state is a CC state in the target excitation space. In this paper, we derive CP series for excitation energies in orders of the CC parent-state similarity-transformed fluctuation potential where the zeroth-order term in the series is an excitation energy for the CC parent state response eigenvalue equation and where the series formally converge to an excitation energy for the CC target state response eigenvalue equation. We give explicit expressions for the lowest-order excitation energy corrections. We also report calculations for CP excitation energy series for various parent and target excitation spaces and examine how well the lower-order corrections can reproduce the total excitation energies. Considering the fast local convergence we have observed for the CP excitation energy series, it becomes computationally attractive to use low-order corrections in CP series to obtain excitation energies of CC target state quality. For the CPS(D-n) series, the first-order correction vanishes, the second-order correction becomes the CIS(D) model, and for the CPS(D-3) model, our calculations suggest that excitation energies of CCSD quality are obtained. The numerical results also suggest that a similar behavior can be seen for the low-order excitation energy corrections for CP series where the parent state contains more than a singles excitation space, e.g., for the CPSD(T) model. We therefore expect the low-order excitation energy corrections in CP series soon to become state-of-the-art models for determining excitation energies of CC target state quality.

OriginalsprogEngelsk
Artikelnummer134109
TidsskriftJournal of Chemical Physics
Vol/bind150
Nummer13
ISSN0021-9606
DOI
StatusUdgivet - 2019

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