Excited-State-Specific Pseudoprojected Coupled-Cluster Theory
Harrison Tuckman, Eric Neuscamman
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.
Topics & Concepts
Excited stateCoupled clusterWave functionRydberg formulaScalingGround statePhysicsAtomic physicsAtomic orbitalPerturbation theory (quantum mechanics)Cluster (spacecraft)Valence (chemistry)Quantum mechanicsStatistical physicsComputer scienceMoleculeMathematicsElectronIonizationGeometryProgramming languageIonAdvanced Chemical Physics StudiesSpectroscopy and Quantum Chemical StudiesCold Atom Physics and Bose-Einstein Condensates