How can one work towards a more predictive, robust use of computational procedures for chemical simulations? Part of the solution is understanding the caveats of current methods, starting with the electronic structure. In this project, we explore a series of local orbital descriptions to analyze and diagnose wave function and density functional theory approaches in the computation of a wide range of properties and systems, ranging from non-covalent interactions in the gas phase to chemical reactivity in solution. Successful applicants will come in contact with state-of-the-art electronic structure methods and embedding techniques for the description of molecules in condensed phases.