A Density Functional Extension to Excited State Mean-Field Theory

Abstract

We investigate an extension of excited state mean-field theory in which the energy expression is augmented with density functional components in an effort to include the effects of weak electron correlations. The approach remains variational and entirely time-independent, allowing it to avoid some of the difficulties associated with linear response and the adiabatic approximation. In particular, all of the electrons' orbitals are relaxed state specifically and there is no reliance on Kohn-Sham orbital energy differences, both of which are important features in the context of charge transfer. Preliminary testing shows clear advantages for single-component charge transfer states, but the method, at least in its current form, is less reliable for states in which multiple particle-hole transitions contribute significantly.

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• A Self Consistent Field Formulation of Excited State Mean Field Theory
• Orbital-optimized versus time-dependent density functional calculations of intramolecular charge transfer excited states
• An N${}^5$-scaling excited-state-specific perturbation theory
• Core Excitations with Excited State Mean Field and Perturbation Theory
• Seniority and Hierarchy Configuration Interaction for Radicals and Excited States
• Excited State Mean-Field Theory without Automatic Differentiation
• Aufbau Suppressed Coupled Cluster Theory for Electronically Excited States
• Freeze-and-release direct optimization method for variational calculations of excited electronic states
• Double Configuration Interaction Singles: Scalable and size-intensive approach for orbital relaxation in excited states and bond-dissociation
• Self-consistent Møller-Plesset Perturbation Theory For Excited States
• One-Body Properties and Their Perturbative Accuracy with Aufbau Suppressed Coupled Cluster Theory