An Introduction to the Electronic Structure of Atoms and Molecules

Dr. Richard F.W. Bader
Professor of Chemistry / McMaster University / Hamilton, Ontario

1.  The Nature of the Problem
2.  The New Physics
3.  The Hydrogen Atom
4.  Many-Electron Atoms
5.  Electronic Basis for the Properties of the Elements
6. The Chemical Bond
    An Electrostatic Interpretation of the Chemical Bond
    The Effect of the Pauli Principle on Chemical Binding
    The Quantum Mechanical Explanation of Valency
    Molecular Geometry
    Literature References
7.  Ionic and Covalent Binding
8.  Molecular Orbitals
Table of Contour Values

The Effect of the Pauli Principle on Chemical Binding

The Pauli exclusion principle plays as important a role in the understanding of the electronic structure of molecules as it does in the case of atoms. The end result of the Pauli principle is to limit the amount of electronic charge density that can be placed at any one point in space. For example, the Pauli principle prevents the 1s orbital in an atom from containing more than two electrons. Since the 1s orbital places most of its charge density in regions close to the nucleus, the Pauli principle, by limiting the occupation of the 1s orbital, limits the amount of density close to the nucleus. Any remaining electrons must be placed in orbitals which concentrate their charge density further from the nucleus.

   In an earlier discussion we pointed out that the reason the electron doesn't fall onto the nucleus is because it must possess kinetic energy if Heisenberg's uncertainty principle is not to be violated. This is one reason why matter doesn't collapse. The Pauli principle is equally important in this regard. The electron density of the outer electrons in an atom cannot collapse and move closer to the nucleus since it can do so only if the electrons occupy an orbital with a lower n value. If, however, the inner orbital contains two electrons, then the Pauli principle states that the collapse cannot occur. We must be careful in our interpretation of this aspect of the Pauli principle. The density from a 2s orbital has a small but finite probability of being found well within the density of the 1s orbital. Do not interpret the Pauli principle as implying that the density from an occupied orbital has a clearly defined and distinct region in real space all to its own. This is not the case. The operation of the Pauli principle is more subtle than this. In some simple cases, such as the ones we wish to discuss below, the limiting effect of the Pauli principle on the density distribution can, however, be calculated and pictured in a very direct manner.

   The Pauli principle demands that when two electrons are placed in the same orbital their spins must be paired. What restriction is placed on the spins of the electrons during the formation of a molecule, when two orbitals, each on a different atom, overlap one another? For example, consider the approach of two hydrogen atoms to form a hydrogen molecule. Consider atom A to have the configuration 1s1(­)and atom B the configuration 1s1(¯). Even when the atoms approach very close to one another the Pauli principle would be satisfied as the spins of the two electrons are opposed. This is the situation we have tacitly assumed in our previous discussion of the hydrogen molecule. However, what would occur if two hydrogen atoms approached one another and both had the same configuration and spin, say 1s1(­)? When two atoms are relatively close together the electrons become indistinguishable. It is no longer possible to say which electron is associated with which atom as both electrons move in the vicinity of both nuclei. Indeed this is the effect which gives rise to the chemical bond. In so far as we can still regard the region around each atom to be governed by its own atomic orbital, distorted as it may be, two electrons with the same spin will not be able to concentrate their density in the binding region. This region is common to the orbitals on both atoms, and since the electrons possess the same spin they cannot both be there simultaneously. In the region of greatest overlap of the orbitals, the binding region, the presence of one electron will tend to exclude the presence of the other if their spins are parallel. Instead of density accumulating in the binding region as two atoms approach, electron density is removed from this region and placed in the antibinding region behind each nucleus where the overlap of the orbitals is much smaller. Thus the approach of two hydrogen atoms with parallel spins does not result in the formation of a stable molecule. This repulsive state of the hydrogen molecule, in which both electrons have the same spin and atomic orbital quantum numbers, can be detected spectroscopically.

    We can now give the general requirements for the formation of a chemical bond. Electron density must be accumulated in the region between the nuclei to an extent greater than that obtained by allowing the original atomic density distributions to overlap. In general, the increase in charge density necessary to balance the nuclear force of repulsion requires the presence of two electrons. (Click here for note.)

In the atomic orbital approximation we picture the bond as resulting from the overlap of two distorted atomic orbitals, one centred on each nucleus. When the orbitals overlap, both electrons may move in the field of either nuclear charge as the electrons may now exchange orbitals. Finally, the pair of electrons must possess opposed spins. When their spins are parallel, the charge density from each electron is accumulated in the antibinding rather than in the binding region.

    We shall now apply these principles to a number of examples and in doing so obtain a quantum mechanical definition of valency.