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Maximum overlap methods are effective tools for optimizing challenging ground‐ and excited‐state wave functions using self‐consistent field models such as Hartree‐Fock and Kohn‐Sham density functional theory. Nevertheless, such models have shown significant sensitivity to the user‐defined initial guess of the target wave function. In this work, a projection operator framework is defined and used to provide a metric for non‐aufbau orbital selection in maximum‐overlap‐methods. The resulting algorithms, termed the Projection‐based Maximum Overlap Method (PMOM) and Projection‐based Initial Maximum Overlap Method (PIMOM), are shown to perform exceptionally well when using simple user‐defined target solutions based on occupied/virtual molecular orbital permutations. This work also presents a new metric that provides a simple and conceptually convenient measure of agreement between the desired target and the current or final SCF results during a calculation employing a maximum‐overlap method.

 

Vertical core excitation energies are obtained using a combination of the ΔSCF method and the diagonal second-order self-energy approximation. These methods are applied to a set of neutral molecules and their anionic forms. An assessment of the results with the inclusion of relativistic effects is presented. For core excitations involving delocalized symmetry orbitals, the applied composite method improves upon the overestimation of ΔSCF by providing approximate values close to experimental K-shell transition energies. The importance of both correlation and relaxation contributions to the vertical core-excited state energies, the concept of local and nonlocal core orbitals, and the consequences of breaking symmetry are discussed.