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Further to the previous part [Surf. Rev. Lett. S(3/4), 367 (2001)], this part deals with VLEED numerical quantification of the Cu[sub 3]O[sub 2] bond-forming kinetics on the Cu(001) surface. Besides the solution-number certainty that has been ensured, the modeling exercises have enabled the full capacity of VLEED to be explored, revealing that the bond geometry and the elastic potential define the shapes of the VLEED fine-structure features while the inelastic potential contributes to the absolute intensity. VLEED, covering the valence band in energy, is found to be able to collect nondestructive information from the top atomic layer, as the inelastic damping dominates in this region. Except for the bond geometry, dislocation of a single atom in the unit cell produces no feature that can match the VLEED spectral change, indicating the essentiality of the parametrization techniques developed. It is the right premise that it has enabled the four-stage O-Cu(001) reaction kinetics, revealed by VLEED, to be quantified as the evolution of the CuO[sub 2] to the Cu[sub 3]O[sub 2]. In addition, it is revealed that annealing provides disturbance rather than driving force strengthening the bond energy. Therefore, formulation in terms of bond making and its consequence on the behavior of atoms and valence electrons, and the corresponding parametrization, are demonstrated to be able to correctly reflect the real process of reaction and the correlation of the parameters as well as their natural link to the observations using LEED, STM and PES, or equivalent approaches. [ABSTRACT FROM AUTHOR]

This work consists of two sequential parts, which review the advances in uncovering the capacity of VLEED, STM and PES in revealing the nature and kinetics of oxidation bonding and its consequences for the behavior of atoms and valence electrons at a surface; and in quantifying the O-Cu(001) bonding kinetics. The first part describes the model in terms of bond making and its effect on the valence DOS and on the surface potential barrier (SPB) for surfaces with chemisorbed oxygen. One can replace the hydrogen in a H[sub 2]O molecule with an arbitrary less electronegative element and extend the M[sub 2]O to a solid surface with Goldschmidt contraction of the bond length, which formulates a specific oxidation surface with identification of atomic valences and their correspondence to the STM and PES signatures. As consequences of bond making, oxygen derives four additional DOS features in the valence band and above, i.e. O-M bonding (∼ -5 eV), oxygen nonbonding lone pairs (∼ -2 eV), holes (≤ E[sub F]), and antibonding metal dipoles (≥ E[sub F]), in addition to the hydrogen-bond-like formation. The evolution of O[sup -1] to O[sup -2] transforms the CuO[sub 2] pairing off-centered pyramid in the c(2 × 2)-2O[sup -1] into the Cu[sub 3]O[sub 2] pairing tetrahedron in the (2 √2 × √2)R45°-2O[sup -2] phase on the Cu(001) surface. The new decoding technique has enabled the model to be justified and hence the capacity of VLEED, PES and STM to be fully uncovered in determining simultaneously the bond geometry, the SPB, the valence DOS, and their interdependence. [ABSTRACT FROM AUTHOR]