MO theory of bonding in metallic substances

The majority of elemental substances, and a large number of compounds, have metallic properties (see Section 3.3). Metallic elemental substances are characterised by three-dimensional structures with high coordination numbers. For example, Na(s) has a body-centred cubic (bcc) structure in which each atom is surrounded by eight others at the corners of a cube, each at a distance of 371.6pm from the atom at the centre. The Na atom also has six next-nearest neighbours in the form of an octahedron, with Na-Na distances of 429.1pm. A fragment of this lattice is shown in Fig. 7.14. These distances may be compared with the Na-Na bond length of 307.6 pm in the Na2 molecule, which can be studied in the gas phase by vaporisation of sodium metal. 

A satisfactory theory of metallic bonding must account for the characteristic properties of high electrical and thermal conductivity, metallic lustre, ductility and the complex magnetic properties of metals which imply the presence of unpaired electrons. The theory should also rationalise the enthalpies of atomisation A/f tom of metallic elemental substances. A/f tom is a measure of the cohesive energy within the solid, and we saw in Chapter 5 how it plays an important part in the thermochemistry of ions in solids and solutions. The atomisation enthalpies of elemental substances (metallic and nonmetallic) are collected in Table 7.1. There is a fair correlation between A/Z tom an(J physical properties such as hardness and melting/boiling points. 

The reader is probably familiar with a simple picture of metallic bonding in which we imagine a lattice of cations M + studded in a sea of delocalised electrons, smeared out over the whole crystal. This model can rationalise such properties as malleability and ductility these require that layers of atoms can slide over one another without-undue repulsion. The sea of electrons acts like a lubricating fluid to shield the M + ions from each other. In contrast, distortion of an ionic structure will necessarily lead to increased repulsion between ions of like charge while deformation of a molecular crystal disrupts the Van der Waals forces that hold it together. It is also easy to visualise the electrical properties of metals in 

Clearly, s-p mixing will have a stabilising effect upon the Li2 molecule, although the bonding can be qualitatively described in terms of s-s overlap alone. The dissociation energy of Li2 is only 105 kJ mol-1 compared with the covalent bond energies in Table 6.2, this is rather 

The double-occupancy of the strongly-bonding MOs at the bottom of the band in metallic Li(s) is apparently enough to stabilise the crystal compared with molecular Li2  

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