Absolute bond energies, definition

According to the definition of the work of adhesion Wa in terms of bond energies (equation (1.12) with A = M and B = AO), Wa is proportional to em-ao where em-ao is an average interaction energy between M atoms and oxide ions. Clearly, Wa is proportional to an absolute bond energy while AHf(MO) is proportional to a difference of bond energies. As a result, the interfacial quantity to be used in a correlation with AHc(mo) should not be Wa but the work of immersion W, which, taking into account its definition (equation (1.54)) and expressions (1.9) to (1.11) of <7SV and [Pg.208]

The definitions (22) and (23) don t require ortho-normalized basis functions. But calculated results fairly depends on basis functions. The absolute value of partitioned energy with orthonormalized basis functions is usually larger and seems more reasonable than the counterpart with non-orthonormalized basis functions, like the case of Okada s bond order. The basis functions orthonormalized by Eq. (19) and Eq. (20) are used for the energy partition calculations in the following sections. But systematic and theoretical studies are necessary to clarify the dependence of bond parameters on the basis functions and the optimization of them. 

Absolute rate coefficients and Arrhenius parameters have been obtained for the cycloaddition reaction of S( F2,1,0) atoms with a representative series of olefins and acetylenes. The activation energies are small, and they exhibit a trend with molecular structure which is expected for an electro-philic reagent The A-factors show a definite trend which can be attributed to steric repulsions and a generalized secondary a-isotope effect explained by activated complex theory. Secondary a-H/D kinetic isotope effects have been measured and their origin discussed. Hartree-Fock type MO calculations indicate that the primary product of the S( F) + olefin reaction is a ring-distorted, triplet state thi-irane, with a considerable energy barrier with respect to rotation around the C-C bond. 

To be consistent with an energy-related measure of structural stability N also has to run over all atoms A in the unit cell (or equivalently in the formula unit), in line with the definition of G, rather than - as it is frequently seen - over the unweighted list of distinct atoms, since the absolute influence of a certain bond valence mismatch will increase with the number of symmetry copies inside the unit cell. 

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