B. Higher-Lying (Near-Edge) Transitions. Table 3 reports error statistics for a data set of 20 higherlying, dipole-allowed transitions originating from 1s orbitals for the elements C (8 transitions), N (6 transitions), and O (6 transitions). These are "higher-lying" (or near-edge) transitions in the sense that the final state is not the LUMO. Experimental excitation energies are taken from various sources and details are provided in the Supporting Information. For each of the methods except ∆SCF, the full XAS spectrum is evaluated by populating the LUMO (only) with a fractional electron. As discussed before, these eigenvalue-based approaches easily avoid variational collapse and other convergence issues that can plague higher-lying near-edge calculations pursued by the ∆SCF approach. Furthermore, a stateby-state calculation is not required.