The 14th International Conference on
Miniaturized Systems for Chemistry and Life Sciences
Electronic configurations describe each electron as moving independently in an orbital, in an average field created by all other orbitals. Mathematically, configurations are described by Slater determinants or configuration state functions.
Knowledge of the electron configuration of different atoms is useful in understanding the structure of the periodic table of elements. This is also useful for describing the chemical bonds that hold atoms together. In bulk materials, this same idea helps explain the peculiar properties of lasers and semiconductors.
The energy associated to an electron is that of its orbital. The energy of a configuration is often approximated as the sum of the energy of each electron, neglecting the electron-electron interactions. The configuration that corresponds to the lowest electronic energy is called the ground state. Any other configuration is an excited state.
The following year, E. C. Stoner incorporated Sommerfeld's third quantum number into the description of electron shells, and correctly predicted the shell structure of sulfur to be 2.8.6. However neither Bohr's system nor Stoner's could correctly describe the changes in atomic spectra in a magnetic field (the Zeeman effect).
The outermost electron shell is often referred to as the "valence shell" and (to a first approximation) determines the chemical properties. It should be remembered that the similarities in the chemical properties were remarked on more than a century before the idea of electron configuration. It is not clear how far Madelung's rule explains (rather than simply describes) the periodic table, although some properties (such as the common +2 oxidation state in the first row of the transition metals) would obviously be different with a different order of orbital filling.
The fact that the Aufbau principle is based on an approximation can be seen from the fact that there is an almost-fixed filling order at all, that, within a given shell, the s-orbital is always filled before the p-orbitals. In a hydrogen-like atom, which only has one electron, the s-orbital and the p-orbitals of the same shell have exactly the same energy, to a very good approximation in the absence of external electromagnetic fields. (However, in a real hydrogen atom, the energy levels are slightly split by the magnetic field of the nucleus, and by the quantum electrodynamic effects of the Lamb shift.)
The apparent paradox arises when electrons are removed from the transition metal atoms to form ions. The first electrons to be ionized come not from the 3d-orbital, as one would expect if it were "higher in energy", but from the 4s-orbital. This interchange of electrons between 4s and 3d is found for all atoms of the first series of transition metals. The configurations of the neutral atoms (K, Ca, Sc, Ti, V, Cr, ...) usually follow the order 1s, 2s, 2p, 3s, 3p, 4s, 3d, ...; however the successive stages of ionization of a given atom (such as Fe4+, Fe3+, Fe2+, Fe+, Fe) usually follow the order 1s, 2s, 2p, 3s, 3p, 3d, 4s, ...
The most widespread application of electron configurations is in the rationalization of chemical properties, in both inorganic and organic chemistry. In effect, electron configurations, along with some simplified form of molecular orbital theory, have become the modern equivalent of the valence concept, describing the number and type of chemical bonds that an atom can be expected to form.
This approach is taken further in computational chemistry, which typically attempts to make quantitative estimates of chemical properties. For many years, most such calculations relied upon the "linear combination of atomic orbitals" (LCAO) approximation, using an ever-larger and more complex basis set of atomic orbitals as the starting point. The last step in such a calculation is the assignment of electrons among the molecular orbitals according to the Aufbau principle. Not all methods in calculational chemistry rely on electron configuration: density functional theory (DFT) is an important example of a method that discards the model.
. For atoms or molecules with more than one electron, the motion of electrons are correlated and such a picture is no longer exact. A very large number of electronic configurations are needed to exactly describe any multi-electron system, and no energy can be associated with one single configuration. However, the electronic wave function is usually dominated by a very small number of configurations and therefore the notion of electronic configuration remains essential for multi-electron systems.
A fundamental application of electron configurations is in the interpretation of atomic spectra. In this case, it is necessary to supplement the electron configuration with one or more term symbols, which describe the different energy levels available to an atom. Term symbols can be calculated for any electron configuration, not just the ground-state configuration listed in tables, although not all the energy levels are observed in practice. It is through the analysis of atomic spectra that the ground-state electron configurations of the elements were experimentally determined.