A combination of the photoelectron spectrometrics and density functional theory calculations has confirmed bond-order-length-strength (BOLS) predictions on the atomic undercoordination induced local bond contraction, charge densification and bond energy entrapment of lithium (Li) atomic clusters and layer-resolved Li(1 1 0) skins. Analysis also derives the energy level of an isolated Li atom and its shift upon bulk and skin formation, which is beyond the scope of currently available approaches. (C) 2015 Elsevier B.V. All rights reserved.