Atomic radius

In 1920, shortly after it had become possible to determine the sizes of atoms using X-ray crystallography, it was suggested that all atoms of the same element have the same radii.[3] However, in 1923, when more crystal data had become available, it was found that the approximation of an atom as a sphere does not necessarily hold when comparing the same atom in different crystal structures.[4]

Widely used definitions of atomic radius include:

• Van der Waals radius: In the simplest definition, half the minimum distance between the nuclei of two atoms of the element that are not otherwise bound by covalent or metallic interactions.[5] The Van der Waals radius may be defined even for elements (such as metals) in which Van der Waals forces are dominated by other interactions. Because Van der Waals interactions arise through quantum fluctuations of the atomic polarisation, the polarisability (which can usually be measured or calculated more easily) may be used to define the Van der Waals radius indirectly.[6]

• Ionic radius: the nominal radius of the ions of an element in a specific ionization state, deduced from the spacing of atomic nuclei in crystalline salts that include that ion. In principle, the spacing between two adjacent oppositely charged ions (the length of the ionic bond between them) should equal the sum of their ionic radii.[5]
• Covalent radius: the nominal radius of the atoms of an element when covalently bound to other atoms, as deduced from the separation between the atomic nuclei in molecules. In principle, the distance between two atoms that are bound to each other in a molecule (the length of that covalent bond) should equal the sum of their covalent radii.[5]
• Metallic radius: the nominal radius of atoms of an element when joined to other atoms by metallic bonds.
• Bohr radius: the radius of the lowest-energy electron orbit predicted by Bohr model of the atom (1913).[7][8] It is only applicable to atoms and ions with a single electron, such as hydrogen, singly ionized helium, and positronium. Although the model itself is now obsolete, the Bohr radius for the hydrogen atom is still regarded as an important physical constant, because it is equivalent to the quantum-mechanical most probable distance of the electron from the nucleus.

The following table shows empirically measured covalent radii for the elements, as published by J. C. Slater in 1964.[9] The values are in picometers (pm or 1×10⁻¹² m), with an accuracy of about 5 pm. The shade of the box ranges from red to yellow as the radius increases; gray indicates lack of data.

A graph comparing the atomic radius of elements with atomic numbers 1–100. Accuracy of ±5 pm.

The way the atomic radius varies with increasing atomic number can be explained by the arrangement of electrons in shells of fixed capacity. The shells are generally filled in order of increasing radius, since the negatively charged electrons are attracted by the positively charged protons in the nucleus. As the atomic number increases along each row of the periodic table, the additional electrons go into the same outermost shell; whose radius gradually contracts, due to the increasing nuclear charge. In a noble gas, the outermost shell is completely filled; therefore, the additional electron of next alkali metal will go into the next outer shell, accounting for the sudden increase in the atomic radius.

The increasing nuclear charge is partly counterbalanced by the increasing number of electrons, a phenomenon that is known as shielding; which explains why the size of atoms usually increases down each column. However, there is one notable exception, known as the lanthanide contraction: the 5d block of elements are much smaller than one would expect, due to the weak shielding of the 4f electrons.

Essentially, the atomic radius decreases across the periods due to an increasing number of protons. Therefore, there is a greater attraction between the protons and electrons because opposite charges attract, and more protons create a stronger charge. The greater attraction draws the electrons closer to the protons, decreasing the size of the particle. Therefore, the atomic radius decreases. Down the groups, atomic radius increases. This is because there are more energy levels and therefore a greater distance between protons and electrons. In addition, electron shielding causes attraction to decrease, so remaining electrons can go farther away from the positively charged nucleus. Therefore, the size, or atomic radius, increases.

The following table summarizes the main phenomena that influence the atomic radius of an element:

The following table shows atomic radii computed from theoretical models, as published by Enrico Clementi and others in 1967.[11] The values are in picometres (pm).

• Atomic radii of the elements (data page)
• Chemical bond
• Covalent radius
• Bond length
• Steric hindrance
• Kinetic diameter

• Difference between empirical and calculated data: Empirical data means "originating in or based on observation or experience" or "relying on experience or observation alone often without due regard for system and theory data".[12] In other words, the data are measured through physical observation, and vetted by other experiments generating similar results. Calculated data, on the other hand, are derived from theoretical models. Such predictions are especially useful for elements whose radii cannot be measured experimentally (e.g. those that have not been discovered, or that have too short of a half-life).