Absolute core-level binding energy shifts between atom and solid: The Born-Haber cycle revisited for free nanoscale metal clusters

Abstract in Undetermined
Core-level binding energy shifts between the free atomand corresponding large clusters, the latter closely
approximating the infinite solid, have been experimentally derived for several elemental metals. The
cluster core-level binding energies in question have been determined relative to the vacuum level using
synchrotron-based photoelectron spectroscopy. As expected, the experimental shift values show reasonable
agreement with those calculated using the thermochemical Born–Haber cycle approach. The largest
uncertainty factors defining the discrepancies between the experiment and the model, such as the difference
in the multiplet structure of free atoms and the solid, the in some cases indirectly established cluster
work functions, and the metal solvation energy, are discussed.