Among the approaches examined, composite methods that couple moderate-cost DFT geometry optimizations with DLPNO-CCSD(T)-F12d single-point energy calculations deliver superior accuracy over a broad range of species. For neutral singlets, lower-level geometry optimizations (e.g., B97-1/6-31G(D) or GFN2-xTB) are sufficient to maintain good accuracy while lowering computational cost. However, more complex species -such as anions, cations, zwitterions, doublets, and triplets -benefit from a robust yet still moderate DFT level (e.g., ωB97X-D/def2-TZVPD) to balance accuracy and cost. When a single-step DFT solution is preferred for convenience, functionals including ωB97X-D and M06-2X remain viable options, albeit typically yield higher errors.