Symmetry-separated models

Symmetry-separated (a+rr) vs bent-bond (Q) models of first-row transition-metal methylene cations 281... 

Fig. 8. Diffraction space according to the "disordered stacking model" (a) achiral (zigzag) tube (b) chiral tube. The parallel circles represent the inner rims of diffuse coronae, generated by streaked reflexions. The oo.l nodes generate sharp circles. In (a) two symmetry related 10.0 type nodes generate one circle. In the chiral case (b) each node generates a separate corona [9].

Fig. 13. Simulated diffraction space of a 10-layer monochiral MWCNT with Hamada indices (40+8/ , 5+k) with / =0,...,9. In (a), (a ) and (02) the initial stacking at ( q was ABAB. whereas in (b), (b[) and (b2) the initial stacking was random, (a) The normal incidence pattern has a centre of symmetry only. (3 )(a2) The cusps are of two different types. The arc length separating the cusps is c (b) The normal incidence pattern now exhibits 2mm symmetry. (b )(b2) The cusps are distributed at random along the generating circles of the evolutes. These sections represent the diffuse coronae referred to in the "disordered stacking model" [17].

Eq. (22) have been derived from the variation principle alone (given the structure of H) they contain only the single model approximation of Eq. (9) the typically chemical idea that the electronic structure of a complex many-electron system can be (quantitatively as well as qualitatively) understood in terms of the interactions among conceptually identifiable separate electron groups. In the discussion of the exact solutions of the Schrodinger equation for simple systems the operators which commute with the relevant H ( symmetries ) play a central role. We therefore devote the next section to an examination of the effect of symmetry constraints on the solutions of (22). 

In everything that follows in this section we tacitly use a realistic model for the molecular electronic structure at all internuclear separations (e.g. UHF or electron-pair). Deferring questions of numerical techniques for the moment to a later section, we can investigate these functions as basis functions for the calculation of molecular electronic structure and investigate the spatial symmetry constraint in a wider context than the hydrogen molecule. 

The most widely used qualitative model for the explanation of the shapes of molecules is the Valence Shell Electron Pair Repulsion (VSEPR) model of Gillespie and Nyholm (25). The orbital correlation diagrams of Walsh (26) are also used for simple systems for which the qualitative form of the MOs may be deduced from symmetry considerations. Attempts have been made to prove that these two approaches are equivalent (27). But this is impossible since Walsh s Rules refer explicitly to (and only have meaning within) the MO model while the VSEPR method does not refer to (is not confined by) any explicitly-stated model of molecular electronic structure. Thus, any proof that the two approaches are equivalent can only prove, at best, that the two are equivalent at the MO level i.e. that Walsh s Rules are contained in the VSEPR model. Of course, the transformation to localised orbitals of an MO determinant provides a convenient picture of VSEPR rules but the VSEPR method itself depends not on the independent-particle model but on the possibility of separating the total electronic structure of a molecule into more or less autonomous electron pairs which interact as separate entities (28). The localised MO description is merely the simplest such separation the general case is our Eq. (6)... 

We have not mentioned open shells of electrons in our general considerations but then we have not specifically mentioned closed shells either. Certainly our examples are all closed shell but this choice simply reflects our main area of interest valence theory. The derivations and considerations of constraints in the opening sections are independent of the numbers of electrons involved in the system and, in particular, are independent of the magnetic properties of the molecules concerned simply because the spin variable does not occur in our approximate Hamiltonian. Nevertheless, it is traditional to treat open and closed shells of electrons by separate techniques and it is of some interest to investigate the consequences of this dichotomy. The independent-electron model (UHF - no symmetry constraints) is the simplest one to investigate we give below an abbreviated discussion. 

---