Electron configuration

The electron configuration or organisation of electrons orbiting neutral atoms shows a recurring pattern or periodicity. The electrons occupy a series of electron shells (numbered shell 1, shell 2, and so on). Each shell consists of one or more subshells (named s, p, d, f and g). As atomic number increases, electrons progressively fill these shells and subshells more or less according to the Madelung rule or energy ordering rule, as shown in the diagram. The electron configuration for neon, for example, is 1s2 2s2 2p6. With an atomic number of ten, neon has two electrons in the first shell, and eight electrons in the second shell—two in the s subshell and six in the p subshell. In periodic table terms, the first time an electron occupies a new shell corresponds to the start of each new period, these positions being occupied by hydrogen and the alkali metals.

Periodic table trends (arrows show an increase)

Since the properties of an element are mostly determined by its electron configuration, the properties of the elements likewise show recurring patterns or periodic behaviour, some examples of which are shown in the diagrams below for atomic radii, ionization energy and electron affinity. It is this periodicity of properties, manifestations of which were noticed well before the underlying theory was developed, that led to the establishment of the periodic law (the properties of the elements recur at varying intervals) and the formulation of the first periodic tables.

Atomic radii vary in a predictable and explainable manner across the periodic table. For instance, the radii generally decrease along each period of the table, from the alkali metals to the noble gases; and increase down each group. The radius increases sharply between the noble gas at the end of each period and the alkali metal at the beginning of the next period. These trends of the atomic radii (and of various other chemical and physical properties of the elements) can be explained by the electron shell theory of the atom; they provided important evidence for the development and confirmation of quantum theory.
The electrons in the 4f-subshell, which is progressively filled from cerium (element 58) to ytterbium (element 70), are not particularly effective at shielding the increasing nuclear charge from the sub-shells further out. The elements immediately following the lanthanides have atomic radii that are smaller than would be expected and that are almost identical to the atomic radii of the elements immediately above them.Hence hafnium has virtually the same atomic radius (and chemistry) as zirconium, and tantalum has an atomic radius similar to niobium, and so forth. This is known as the lanthanide contraction. The effect of the lanthanide contraction is noticeable up to platinum (element 78), after which it is masked by a relativistic effect known as the inert pair effect. The d-block contraction, which is a similar effect between the d-block and p-block, is less pronounced than the lanthanide contraction but arises from a similar cause.

The first ionization energy is the energy it takes to remove one electron from an atom, the second ionization energy is the energy it takes to remove a second electron from the atom, and so on. For a given atom, successive ionization energies increase with the degree of ionization. For magnesium as an example, the first ionization energy is 738 kJ/mol and the second is 1450 kJ/mol. Electrons in the closer orbitals experience greater forces of electrostatic attraction; thus, their removal requires increasingly more energy. Ionization energy becomes greater up and to the right of the periodic table.

Large jumps in the successive molar ionization energies occur when removing an electron from a noble gas (complete electron shell) configuration. For magnesium again, the first two molar ionization energies of magnesium given above correspond to removing the two 3s electrons, and the third ionization energy is a much larger 7730 kJ/mol, for the removal of a 2p electron from the very stable neon-like configuration of Mg2+. Similar jumps occur in the ionization energies of other third-row atoms.