Correlation of inner shell binding energies with shifts of charge transfer bands

Inner shell binding energies were determined for the elements in the crystalline compounds A^IIIX^VO₄ where A  B, Al, Ga, Fe and X  P, As with fourfold coordination of A, and in the corresponding dihydrates of Al having a sixfold coordination of Al. The O 1s binding energies for the dihydrates could be resolved into two bands arising from XO₄ -groups and from the water molecules respectively. The O 1s binding energies from the XO₄ groups decrease by about 0.6 eV in going from the anhydrous compounds to their dihydrates whereas the Al 2p binding energies remain constant within the limits of error. These results correlate surprisingly well with shifts of the first charge transfer band of trivalent iron in these compounds. The binding energy differences between phosphates and arsenates are also in good agreement with concurrent shifts of this charge transfer band. The consequences of these results for the concept of optical electronegativities are discussed.