In chemistry, molecular symmetry describes the symmetry present in molecules and the classification of these molecules according to their symmetry. Molecular symmetry is a fundamental concept in chemistry, as it can be used to predict or explain many of a molecule's chemical properties, such as whether or not it has a dipole moment, as well as its allowed spectroscopic transitions. To do this it is necessary to use group theory. This involves classifying the states of the molecule using the irreducible representations from the character table of the symmetry group of the molecule. Symmetry is useful in the study of molecular orbitals, with applications to the Hückel method, to ligand field theory, and to the Woodward-Hoffmann rules. Many university level textbooks on physical chemistry, quantum chemistry, spectroscopy and inorganic chemistry discuss symmetry. Another framework on a larger scale is the use of crystal systems to describe crystallographic symmetry in bulk materials.
There are many techniques for determining the symmetry of a given molecule, including X-ray crystallography and various forms of spectroscopy. Spectroscopic notation is based on symmetry considerations.
Point group symmetry concepts
Elements
The point group symmetry of a molecule is defined by the presence or absence of 5 types of symmetry element.
Symmetry axis: an axis around which a rotation by results in a molecule indistinguishable from the original. This is also called an n-fold rotational axis and abbreviated Cn. Examples are the C2 axis in water and the C3 axis in ammonia. A molecule can have more than one symmetry axis; the one with the highest n is called the principal axis, and by convention is aligned with the z-axis in a Cartesian coordinate system. Plane of symmetry: a plane of reflection through which an identical copy of the original molecule is generated. This is also called a mirror plane and abbreviated σ (sigma = Greek "s", from the German 'Spiegel' meaning mirror). Water has two of them: one in the plane of the molecule itself and one perpendicular to it. A symmetry plane parallel with the principal axis is dubbed vertical (σv) and one perpendicular to it horizontal (σh). A third type of symmetry plane exists: If a vertical symmetry plane additionally bisects the angle between two 2-fold rotation axes perpendicular to the principal axis, the plane is dubbed dihedral (σd). A symmetry plane can also be identified by its Cartesian orientation, e.g., (xz) or (yz). Center of symmetry or inversion center, abbreviated i. A molecule has a center of symmetry when, for any atom in the molecule, an identical atom exists diametrically opposite this center an equal distance from it. In other words, a molecule has a center of symmetry when the points (x,y,z) and (−x,−y,−z) are identical. For example, if there is an oxygen atom in some point (x,y,z), then there is an oxygen atom in the point (−x,−y,−z). There may or may not be an atom at the inversion center itself. Examples are xenon tetrafluoride where the inversion center is at the Xe atom, and benzene () where the inversion center is at the center of the ring. Rotation-reflection axis: an axis around which a rotation by , followed by a reflection in a plane perpendicular to it, leaves the molecule unchanged. Also called an n-fold improper rotation axis, it is abbreviated Sn. Examples are present in tetrahedral silicon tetrafluoride, with three S4 axes, and the staggered conformation of ethane with one S6 axis. An S1 axis corresponds to a mirror plane σ and an S2 axis is an inversion center i. A molecule which has no Sn axis for any value of n is a chiral molecule. Identity, abbreviated to E, from the German 'Einheit' meaning unity. This symmetry element simply consists of no change: every molecule has this symmetry element, which is equivalent to a C1 proper rotation. It must be included in the list of symmetry elements so that they form a mathematical group, whose definition requires inclusion of the identity element. It is so called because it is analogous to multiplying by one (unity).