A Mean Field Platform for Excited State Quantum Chemistry

Abstract

We present a mean field theory for excited states that is broadly analogous to ground state Hartree-Fock theory. Like Hartree-Fock, our approach is deterministic, state-specific, applies a variational principle to a minimally correlated ansatz, produces energy stationary points, relaxes the orbital basis, has a Fock-build cost-scaling, and can serve as the foundation for correlation methods such as perturbation theory and coupled cluster theory. To emphasize this last point, we pair our mean field approach with an excited state analogue of second order Moller-Plesset theory and demonstrate that in water, formaldehyde, neon, and stretched lithium fluoride, the resulting accuracy far exceeds that of configuration interaction singles and rivals that of equation of motion coupled cluster.

arXiv comment6 pages

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• Orbital Optimized Density Functional Theory for Electronic Excited States
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• Real time evolution for ultracompact Hamiltonian eigenstates on quantum hardware
• Variational coupled cluster for ground and excited states
• Excited State Specific Multi-Slater Jastrow Wave Functions
• A Density Functional Extension to Excited State Mean-Field Theory
• Excited states, symmetry breaking, and unphysical solutions in state-specific CASSCF theory
• A Self Consistent Field Formulation of Excited State Mean Field Theory
• Generalised Nonorthogonal Matrix Elements: Unifying Wick's Theorem and the Slater-Condon Rules
• State-Specific Coupled-Cluster Methods for Excited States
• Excited-state diffusion Monte Carlo calculations: a simple and efficient two-determinant ansatz
• Exact Excited-State Functionals of the Asymmetric Hubbard Dimer
• Core Excitations with Excited State Mean Field and Perturbation Theory
• An N${}^5$-scaling excited-state-specific perturbation theory
• Seniority and Hierarchy Configuration Interaction for Radicals and Excited States
• Complex Adiabatic Connection: a Hidden Non-Hermitian Path from Ground to Excited States
• An Excited-State-Specific Pseudoprojected Coupled-Cluster Theory
• Generalized nonorthogonal matrix elements for arbitrary excitations
• Excited State Mean-Field Theory without Automatic Differentiation
• Studying excited-state-specific perturbation theory on the Thiel set
• Aufbau Suppressed Coupled Cluster Theory for Electronically Excited States
• Double Configuration Interaction Singles: Scalable and size-intensive approach for orbital relaxation in excited states and bond-dissociation
• 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