An Excited-State-Specific Pseudoprojected Coupled-Cluster Theory

Abstract

We present an excited-state-specific coupled-cluster approach in which both the molecular orbitals and cluster amplitudes are optimized for an individual excited state. The theory is formulated via a pseudoprojection of the traditional coupled-cluster wavefunction that allows correlation effects to be introduced atop an excited state mean field starting point. The approach shares much in common with ground state CCSD, including size extensivity and an $N^6$ cost scaling. Preliminary numerical tests show that, when augmented with $N^5$-cost perturbative corrections for key terms, the method can improve over excited-state-specific second order perturbation theory in valence, charge transfer, and Rydberg states.

arXiv comment17 pages, 2 figures, 9 tables Updated to reflect changes made during peer review process, conclusions remain the same

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• Double Configuration Interaction Singles: Scalable and size-intensive approach for orbital relaxation in excited states and bond-dissociation
• Two Determinant Distinguishable Cluster
• Leveraging configuration interaction singles for qualitative descriptions of ground and excited states: state-averaging, linear-response, and spin-projection
• One-Body Properties and Their Perturbative Accuracy with Aufbau Suppressed Coupled Cluster Theory