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The trend with A-site cation is not surprising in an ionic picture. One can think of the formation energy in stages: first the formation of ions by atomization and ionization of the elements, and then formation of a lattice from the ions. The latter would favor smaller lattice parameters via the 1/r scaling of the Ewald energy (which is opposite to the calculated trends in the energies), but this is overcome by the large ionization and atomization energies. The sums of the experimental atomization, and first and second ionization energies for Be, Mg, Ca, and Sr are 2982, 2336, 1913, and 1778 kJ/mol, respectively; NIST.
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