  A zone-resolved photoelectron spectroscopy (ZPS) has enabled us to gain the
local and quantitative information and hence confirm our theoretical
expectations on the bonding and electronic dynamics at graphite skin with and
without atomic vacancy defects. The ZPS study has revealed: i) the 1s energy
level of an isolated carbon atom is located at 282.57 eV, which shifts by 1.32
eV deeper upon diamond bulk formation; ii) the graphite surface bonds contract
by 18% with 165% gain in energy compared with the C-C bond in the bulk diamond;
the surface C 1s energy shifts 2.08 eV deeper from the 1s level of an isolated
carbon atom; and iii) the defect bonds are ~26% shorter and 215% stronger with
the binding energy shift of ~2.85 eV. An additional polarization peak centered
at 1.28 eV below the C 1s level presents when the vacancy is formed. Associated
with the scanning tunneling microscopy/spectroscopy observations and density
functional theory calculations, the ZPS measurements clarify, for the first
time, that the graphitic Dirac-Fermi polarons at atomic vacancy or graphene
zigzag edge arise from the polarization of the unpaired dangling-bond electrons
by the undercoordination-induced local densification and quantum entrapment of
the bonding electrons.
