A Self Consistent Field Formulation of Excited State Mean Field Theory

Abstract

We show that, as in Hartree Fock theory, the orbitals for excited state mean field theory can be optimized via a self-consistent one-electron equation in which electron-electron repulsion is accounted for through mean field operators. In addition to showing that this excited state ansatz is sufficiently close to a mean field product state to admit a one-electron formulation, this approach brings the orbital optimization speed to within roughly a factor of two of ground state mean field theory. The approach parallels Hartree Fock theory in multiple ways, including the presence of a commutator condition, a one-electron mean-field working equation, and acceleration via direct inversion in the iterative subspace. When combined with a configuration interaction singles Davidson solver for the excitation coefficients, the self consistent field formulation dramatically reduces the cost of the theory compared to previous approaches based on quasi-Newton descent.

arXiv comment6 pages, 3 tables, 1 figure, plus supplementary material

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• An Excited-State-Specific Pseudoprojected Coupled-Cluster Theory
• Generalized nonorthogonal matrix elements for arbitrary excitations
• Studying excited-state-specific perturbation theory on the Thiel set
• Limitations of Hartree-Fock with quantum resources
• 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