Electronic structure methods are now widely used to assist in the interpretation of many varieties of experimental data. The energies and physical characteristics (e.g., sizes, shapes, and spatial localization) of valence antibonding π* and σ* orbitals play key roles in a variety of chemical processes including photochemical reactions and electron attachment reductions and are used in Woodward-Hoffmann-type analyses to probe reaction energy barriers and energy surface intersections leading to internal conversion or intersystem crossings. One's ability to properly populate such valence antibonding orbitals within electronic structure calculations is often hindered by the presence of other molecular orbitals having similar energies. These intruding orbitals can be of Rydberg, pseudo-continuum, or dipole-bound characteristic. This article shows how, within the most widely available electronic structure codes, one can avoid the pitfalls presented by these intruding orbitals to properly populate a valence π* or σ* orbital and how to subsequently use that orbital in a calculation that includes electron correlation effects and thereby offers the possibility of chemically useful precision. Special emphasis is given to cases in which the electronic state is metastable.