Assignments of the calculated XES valence-to-core region based on the orbital character corresponding to the individual transitions for compounds 1 (a), 2 (b), 3a (c) and 3b (d). The left side shows the Kβ″ region, the right side shows the Kβ2,5 region with different intensity scales. Grey areas where transitions of different donor orbital character appear; from left to right: H2Obridge 2s, Osalpn 2s, Nsalpn 2s, Obridge 2s in the left half; OH/OH2 2p and LMCT, Mn-O/Nsalpn and Mn-Obridge in the right half. Transitions from orbitals with OHbridge 2s character are found either in the Osalpn 2s region (mixed with Osalpn 2s character) or separately in the Nsalpn 2s energy region (darkest grey). Representative donor orbitals for each of the spectral regions are shown in Figure 7.