Bonding considerations bond theory

Another approach is spin-coupled valence bond theory, which divides the electrons into two sets core electrons, which are described by doubly occupied orthogonal orbitals, and active electrons, which occupy singly occupied non-orthogonal orbitals. Both types of orbital are expressed in the usual way as a linear combination of basis functions. The overall wavefunction is completed by two spin fimctions one that describes the coupling of the spins of the core electrons and one that deals with the active electrons. The choice of spin function for these active electrons is a key component of the theory [Gerratt ef al. 1997]. One of the distinctive features of this theory is that a considerable amount of chemically significant electronic correlation is incorporated into the wavefunction, giving an accuracy comparable to CASSCF. An additional benefit is that the orbitals tend to be... 

The study of 8-N compounds is one of the most active areas of current inorganic research many novel cyclic and acyclic compounds are being prepared which have unusual stmctures and which pose considerable problems in terms of simple bonding theory. The discoveiy in 1975 that the polymer (8N)jc is a metal whose conductivity increases with decrease in... 

Delocalization occurs in molecules wherever it is possible by symmetry considerations and wherever an energetic advantage can be gained from its operation. MO theory deals very satisfactorily with delocalization, but with valence bond theory the concept is somewhat clumsily incorporated as an addition to the conventional two-electron, two-centre bonding. In general, the stability conferred upon a molecule by delocalization is because the orbitals are more extensive, so that interelectronic repulsion is minimized. 

Inorganic chemistry draws its strength from its great practical utility, and this book presents the subject from the standpoint of applications rather than the customary one of quantum mechanical bonding theory. Since the quintessential subject matter is the properties of the 112 known chemical elements and their compounds, we begin with a consideration of the availability of the commonest elements in the Earth s crust (Table 1.1), hydrosphere (i.e., oceans, lakes, rivers, snowfields, ice caps, and glaciers), and atmosphere, along with brief summary of the production and uses of these elements and their compounds. 

In the case of tt complexes of substituted cyclopentadienones, such as the iron tricarbonyl derivatives prepared by Weiss and H libel (30), qualitative molecular-orbital theory (20) predicted a considerable reduction of the ketonic carbonyl bond order. It was observed that the ketonic carbonyl frequency dropped by as much as 65 cm-1, in agreement with theory. A similar explanation can also be provided in terms of valence bond theory (Fig. 14). It has been suggested that n complexing of arenes such as benzene results in loss of aromaticity of the ring in contrast to the dicyclopentadienyl... 

Covalent bonds can be described with a variety of models, virtually all of which involve symmetry considerations. As a means of illustrating the role of symmetry in bonding theory and laying some foundation for discussions to follow, this section will show the application of symmetry principles in the construction of hybrid orhitals. Since you will have encountered hybridization before now, hut perhaps not in a symmetry context, this provides a ladle introduction to the application of symmetry. You should remember that the basic procedure outlined here (combining appropriate atomic orbitals to make new orbitals) is applicable also to the derivation of molecular orbitals and ligand group orhitals, both of which will be encountered in subsequent chapters. 

The calculated Si=C bond lengths in trans-bent silynes are distinctively shorter than Si=C bond lengths in silenes (i.e. 1.632 A and 1.714 A in HSi=CH and in H2Si=CH2, respectively, at MP2/6-31G )2970. A theoretical analysis in the framework of natural bond theory predicts for 668b and substituted derivatives bond orders for the SiC bond which are intermediate between double and triple bonds with considerable ionic contributions29711 0. 

Other theoretical considerations for synthetic coordination chemistry (isolobal and isoelectronic analogies, chelate, cis and trans effects, factors affecting the acid/ base properties of coordination compounds, bond theories, etc.) are covered in detail in excellent recent monographs [3,34b,104,106] and, for this reason, are not presented in this book. 

As a tribute to Pauling s contributions, I shall restate and summarize some of the implications for bonding theory that arise when the three-electron bond is incorporated as a mainstream component for VB descriptions of the electronic structures of electron-rich molecules. Attention will be focussed on increased-valence structures for molecular systems that involve four-electron three-centre and six-electron four-centre bonding units. However initially, consideration will be given to the one-electron bond, for which Pauling also provided some attention to both the theory and examples of systems that involve this type of bond in their VB structures. As indicated in ref. [8(a)], experimentally one-electron bonds and three-electron bonds are abundant and well-characterized for odd-electron systems. 

To justify such a description within quantum mechanics we are led into a consideration of ionic and covEilent contributions to an approximate wave function. If covalent contributions are minor, the bond is said to be ionic in character, and the electrostatic model is considered to be applicable. Unfortunately, the terms ionic character and covalent character are used with various meanings. This is so, in part, because the rapid development of chemical bond theory has caused a drift of the meanings of these terms over the past two decades. Pauling s definitions, as presented in his book (1585, p. 48), no doubt represent the intent of most workers as of 1940. He concluded that there is a covalent bond between two atoms X and Y if the dissociation energy of X—is the mean of the dissociation energies of X— X and Y— Y. If the dissociation energy of X— Y exceeds this mean, the excess is attributed to additional ionic character of the bond. This criterion furnishes the basis for his scale of electronegativity, and ionic character is inter-... 

Valence-bond theory is over 90% successful in explaining much of the descriptive chemistry of ground states. VB theory is therefore particularly popular among chemists, since it makes use of familiar concepts such as chemical bonds between atoms, resonance hybrids and the like. It can perhaps be characterized as a theory which explains but does not predict. Valence-bond theory fails to account for the triplet ground state of O2 or for the bonding in electron-deficient molecules such as diborane, B2H6. It is not very useful in consideration of excited states, hence for spectroscopy. Many of these deficiencies are remedied by molecular orbital theory, which we take up in the next two chapters. 

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