In chemistry, a lone pair refers to a pair of valence electrons that are not shared with another atom and is sometimes called a non-bonding pair. Lone pairs are found in the outermost electron shell of atoms. They can be identified by using a Lewis structure. Electron pairs are therefore considered lone pairs if two electrons are paired but are not used in chemical bonding. Thus, the number of lone pair electrons plus the number of bonding electrons equals the total number of valence electrons around an atom.
Lone pairs are a concept used in VSEPR theory which explains the shapes of molecules. They are also referred to in the chemistry of Lewis acids and bases. However not all non-bonding pairs of electrons are considered by chemists to be lone pairs. Examples are the transition metals where the non-bonding pairs do not influence molecular geometry and are said to be stereochemically inactive.
- Examples 1
- Angle changes 2
- Lone pairs and dipole moments 3
- Unusual lone pairs 4
- See also 5
- References 6
A single lone pair can be found with atoms in the nitrogen group such as nitrogen in ammonia, two lone pairs can be found with atoms in the chalcogen group such as oxygen in water and the halogens can carry three lone pairs such as in hydrogen chloride.
In VSEPR theory the electron pairs on the oxygen atom in water form the vertices of a tetrahedron with the lone pairs on two of the four vertices. The H–O–H bond angle is with 104.5°, less than the 109° predicted for a tetrahedral angle, and this can be explained by a repulsive interaction between the lone pairs.
The pairs often exhibit a negative polar character with their high charge density and are located closer to the atomic nucleus on average compared to the bonding pair of electrons. The presence of a lone pair decreases the bond angle between the bonding pair of electrons, due to their high electric charge which causes great repulsion between the electrons. They are also used in the formation of a dative bond. For example, the creation of the hydronium (H3O+) ion occurs when acids are dissolved in water and is due to the oxygen atom donating a lone pair to the hydrogen ion.
This can be seen more clearly when looked at in two more common molecules. For example, in carbon dioxide (CO2), the oxygen atoms are on opposite sides of the carbon, whereas in water (H2O) there is an angle between the hydrogen atoms of 104.5º. Due to the repulsive force of the oxygen atom's lone pairs, the hydrogens are pushed further away, to a point where the forces of all electrons on the hydrogen atom are in equilibrium. This is an illustration of the VSEPR theory.
Lone pairs and dipole moments
Lone pairs can make a contribution to a molecule's dipole moment. NH3 has a dipole moment of 1.47 D. As the electronegativity of nitrogen (3.04) is greater than that of hydrogen (2.2) the result is that the N-H bonds are polar with a net negative charge on the nitrogen atom and a smaller net positive charge on the hydrogen atoms. There is also a dipole associated with the lone pair and this reinforces the contribution made by the polar covalent N-H bonds to ammonia's dipole moment. In contrast to NH3, NF3 has a much lower dipole moment of 0.24 D. Fluorine is more electronegative than nitrogen and the polarity of the N-F bonds is opposite to that of the N-H bonds in ammonia, so that the dipole due to the lone pair opposes the N-F bond dipoles, resulting in a low molecular dipole moment.
Unusual lone pairs
A stereochemically active lone pair is also expected for divalent lead and tin ions due to their formal electronic configuration of ns2. In the solid state this results in the distorted metal coordination observed in the litharge structure adopted by both PbO and SnO. The formation of these heavy metal ns2 lone pairs which was previously attributed to intra-atomic hybridization of the metal s and p states has recently been shown to have a strong anion dependence. This dependence on the electronic states of the anion can explain why some divalent lead and tin materials such as PbS and SnTe show no stereochemical evidence of the lone pair and adopt the symmetric rocksalt crystal structure.
In molecular systems the lone pair can also result in a distortion in the coordination of ligands around the metal ion. The lead lone pair effect can be observed in supramolecular complexes of inhibited.
acidic isonitrile groups based on interaction with germaniums empty 4p orbital 
- IUPAC Gold Book definition: lone (electron) pair
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- Lewis base induced tuning of the Ge–Ge bond order in a digermyne G.H.Spikes and P.P.Power Chem. Commun., 2007, 85–87, doi:10.1039/b612202g