Natural Lewis structure energy

In this case the energy of the natural Lewis-structure model... 

Figure 2.4 Components of the Li-F potential-energy curve E R) = E (R) + E(NL>(R), showing the localized natural-Lewis-structure model energy E(L> (circles, left-hand scale) and delocalized non-Lewis correction ,(NL) (squares, right-hand scale). The classical electrostatic estimate E (dotted line) is shown for comparison.

Let us first inquire whether basic criteria for the validity of low-order perturbation theory are actually satisfied in the present case. As described in Section 1.4, the perturbative starting point is an idealized natural Lewis-structure wavefunction (t//,l )) of doubly occupied NBOs. The accuracy of this Lewis-type starting point may be assessed in terms of the percentage accuracy of the variational energy (E) or density (p(l ). as shown for each molecule in Table 3.20. 

Since Lewis-type NBOs typically have (slightly) less than double occupancy, they are not yet true molecular orbitals in the Hartree-Fock sense. Equivalently, one may say that a determinant of doubly-occupied NBOs, the natural Lewis structure wavefunction "Pl = det (cTAB) (crcD) I must have higher energy than the Hartree-Fock MO wavefunction... 

Low-energy resonance structures of a compound provide better descriptions of the compound s electronic nature than do high-energy resonance structures. The rules for evaluating the stability of resonance structures are the same as those for any other Lewis structure. 

Despite of the common reaction mechanism, peroxo complexes exhibit very different reactivities - as shown by the calculated activation energies -depending on the particular structure (nature of the metal center, peroxo or hydroperoxo functionalities, type and number of ligands). We proposed a model [72, 80] that is able to qualitatively rationalize differences in the epoxidation activities of a series of structurally similar TM peroxo compounds CH3Re(02)20-L with various Lewis base ligands L. In this model the calculated activation barriers of direct oxygen transfer from a peroxo group... 

Before 1927 there was no satisfactory theory of the covalent bond. The chemist had postulated the existence of the valence bond between atoms and had built up a body of empirical information about it, but his inquiries into its structure had been futile. The step taken by Lewis of associating two electrons with a bond can hardly be called the development of a theory, since it left unanswered the fundamental questions as to the nature of the interactions involved and the source of the energy of the bond. Only in 1927 was the development of the theory of the covalent bond initiated by the work o Condon28 and of Hertler and London27 on the hydrogen molecule, described in the following paragraphs. 

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