Understanding processes that involve excited states, such as charge transfer and core excitations, is challenging because of the accuracy or efficiency of existing methods. Recent progress in understanding such processes includes the development of a mean-field approach for excited states that is broadly analogous to the Hartree-Fock method for ground states. The current approach in practice (Excited State Mean-Field theory, ESMF) is to optimize a constrained excited state variational principle by Newton or quasi-Newton nonlinear minimization methods, but this requires many Fock builds per iteration of the minimization method. This project aims to further the analogy to Hartree-Fock by reframing these ESMF equations parallel to the Roothan equations as a pseudo-eigenvalue problem with the goal of drastically reducing the number of required Fock builds. We will present a discussion of the theory involved as well as preliminary results for benchmark excited state systems.

Searching for a self consistent field approach to excited state mean field theory

2019 Fall National Meeting

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