The quantum mechanics of bonding

The preceding discussion has outlined the general approach to covalent bonding and has shown how it is still widely employed for a qualitative understanding of molecules. It is incomplete in many respects, however. First, the role of the electron pair remains unexplained but appears to be the hinge of both Lewis’s theory and the VSEPR theory. Second, there is evidence that suggests that Lewis’ theory overemphasizes the role of electron pairs. More fundamentally, little has been said about the distribution of bonding electrons in terms of orbitals, although it has been shown that in atoms the distributions of electrons are described by wave functions. Finally, the models that have been described have little quantitative content: they do not lead to bond lengths or precise bond angles, nor do they give much information about the strengths of bonds.

A full theory of the chemical bond needs to return to the roots of the behaviour of electrons in molecules. That is, the role of the electron pair and the quantitative description of bonding must be based on the Schrödinger equation and the Pauli exclusion principle. This section describes the general features of such an approach. Once again, the discussion will be largely qualitative and conceptual rather than mathematical and numerical. However, the character of the presentation here should not be taken to imply that the current understanding of molecules is not rigorous, quantitative, and precise.

Several difficulties are encountered at the outset of the application of the Schrödinger equation to molecules. Even the simplest molecules consist of two nuclei and several electrons, and interesting molecules may contain a thousand atoms and tens of thousands of electrons. So that any progress of a generally applicable kind can be made, approximations are necessary.

One approximation is common to all discussions of molecules. The Born-Oppenheimer approximation, which was introduced by Max Born and J. Robert Oppenheimer in 1927, separates the motion of the electrons in a molecule from the motion of the nuclei. The separation is based on the fact that the nuclei are much heavier than the electrons and move more slowly. Hence, even though nuclei do move, the electrons can respond to their new positions almost instantaneously. That being the case, it is permissible to consider the nuclei as stationary in a given arrangement and then to solve the Schrödinger equation for the electrons in that stationary framework of nuclei. In order to explore how the energy of the molecule changes as the nuclei change their positions, a series of static nuclear arrangements can be selected, and the Schrödinger equation solved for the electrons in each stationary arrangement.

The data obtained from such a procedure can be used to construct a molecular potential energy curve, a graph that shows how the energy of the molecule varies as bond lengths and bond angles are changed. A typical curve for a diatomic molecule, in which only the internuclear distance is variable, is shown in Figure 10. The energy minimum of this curve corresponds to the observed bond length of the molecule. The depth of the minimum is (apart from a small correction for the vibrational properties of the bond) equal to the bond dissociation energy and hence indicates the tightness with which the two atoms are held together. The steepness of the walls of the curve, which shows how rapidly the energy changes as the nuclear separation changes, indicates the rigidity of the bond. Thus, quantitative information can be obtained from such an approach.

Even the Born-Oppenheimer approximation is only one of the approximations needed for the study of the molecule. It separates out the nuclear motion and leaves untouched the need to solve the Schrödinger equation for several (and perhaps tens of thousands) of electrons. Two major alternative approximations beyond the Born-Oppenheimer approach have been devised to tackle this aspect of the problem. The first to be proposed (by Walter Heitler and Fritz London in 1927 and substantially developed by John Slater and Linus Pauling in the 1930s) is valence bond (VB) theory. This theory introduced language into chemistry that is still widely used, particularly in the discussion of organic compounds, but it has been somewhat overshadowed in quantitative investigations by its rival. The latter, molecular orbital (MO) theory, was introduced in 1927 by Robert S. Mulliken and Friedrich Hund. It has undergone considerable development and is the principal model for the calculation of molecular properties and for general discussions of compounds.