Non-bonding orbital
Encyclopedia
A non-bonding orbital, also known as non-bonding molecular orbital (NBMO) and sometimes designated by the letter n in molecular orbital diagrams, is a molecular orbital
whose occupation by electrons neither increases nor decreases the bond order
between the involved atom
s. Non-bonding orbitals are the equivalent in molecular orbital theory
of the lone pair
s in Lewis structure
s. The energy level
of a non-bonding orbital is typically in between the lower energy of a valence shell bonding orbital and the higher energy of a corresponding antibonding orbital. As such, a non-bonding orbital with electrons would commonly be a HOMO (highest occupied molecular orbital).
According to molecular orbital theory, molecular orbitals are formed from the linear combination of atomic orbitals. In a simple diatomic molecule such as hydrogen fluoride
(chemical formula
: HF), one atom may have many more electrons than the other. A sigma bonding orbital is created between the atomic orbitals with like symmetry. Some orbitals (e.g. px and py orbitals from the fluorine in HF) may not have any other orbitals to combine with and become non-bonding molecular orbitals. In the HF example, the px and py orbitals remain px and py orbitals in shape but when viewed as molecular orbitals are thought of as non-bonding. The energy of the orbital does not depend on the length of any bond within the molecule. Its occupation neither increases nor decreases the stability of the molecule, relative to the atoms, since its energy is the same in the molecule as in one of the atoms. For example, there are two rigorously non-bonding orbitals that are occupied in the ground state of the hydrogen fluoride diatomic molecule; these molecular orbitals are localized on the fluorine atom and are composed of p-type atomic orbital
s whose orientation is perpendicular to the internuclear axis. They are therefore unable to overlap and interact with the s-type valence orbital on the hydrogen atom.
Although non-bonding orbitals are often similar to the atomic orbitals of their constituent atom, they do not need to be similar. An example of a non-similar one is the non-bonding orbital of the allyl
anion, whose electron density is concentrated on the first and third carbon atoms.
Molecular orbital
In chemistry, a molecular orbital is a mathematical function describing the wave-like behavior of an electron in a molecule. This function can be used to calculate chemical and physical properties such as the probability of finding an electron in any specific region. The term "orbital" was first...
whose occupation by electrons neither increases nor decreases the bond order
Bond order
Bond order is the number of chemical bonds between a pair of atoms. For example, in diatomic nitrogen N≡N the bond order is 3, while in acetylene H−C≡C−H the bond order between the two carbon atoms is also 3, and the C−H bond order is 1. Bond order gives an indication to the stability of a bond....
between the involved atom
Atom
The atom is a basic unit of matter that consists of a dense central nucleus surrounded by a cloud of negatively charged electrons. The atomic nucleus contains a mix of positively charged protons and electrically neutral neutrons...
s. Non-bonding orbitals are the equivalent in molecular orbital theory
Molecular orbital theory
In chemistry, molecular orbital theory is a method for determining molecular structure in which electrons are not assigned to individual bonds between atoms, but are treated as moving under the influence of the nuclei in the whole molecule...
of the lone pair
Lone pair
In chemistry, a lone pair is a valence electron pair without bonding or sharing with other atoms. They are found in the outermost electron shell of an atom, so lone pairs are a subset of a molecule's valence electrons...
s in Lewis structure
Lewis structure
Lewis structures are diagrams that show the bonding between atoms of a molecule and the lone pairs of electrons that may exist in the molecule. A Lewis structure can be drawn for any covalently bonded molecule, as well as coordination compounds...
s. The energy level
Energy level
A quantum mechanical system or particle that is bound -- that is, confined spatially—can only take on certain discrete values of energy. This contrasts with classical particles, which can have any energy. These discrete values are called energy levels...
of a non-bonding orbital is typically in between the lower energy of a valence shell bonding orbital and the higher energy of a corresponding antibonding orbital. As such, a non-bonding orbital with electrons would commonly be a HOMO (highest occupied molecular orbital).
According to molecular orbital theory, molecular orbitals are formed from the linear combination of atomic orbitals. In a simple diatomic molecule such as hydrogen fluoride
Hydrogen fluoride
Hydrogen fluoride is a chemical compound with the formula HF. This colorless gas is the principal industrial source of fluorine, often in the aqueous form as hydrofluoric acid, and thus is the precursor to many important compounds including pharmaceuticals and polymers . HF is widely used in the...
(chemical formula
Chemical formula
A chemical formula or molecular formula is a way of expressing information about the atoms that constitute a particular chemical compound....
: HF), one atom may have many more electrons than the other. A sigma bonding orbital is created between the atomic orbitals with like symmetry. Some orbitals (e.g. px and py orbitals from the fluorine in HF) may not have any other orbitals to combine with and become non-bonding molecular orbitals. In the HF example, the px and py orbitals remain px and py orbitals in shape but when viewed as molecular orbitals are thought of as non-bonding. The energy of the orbital does not depend on the length of any bond within the molecule. Its occupation neither increases nor decreases the stability of the molecule, relative to the atoms, since its energy is the same in the molecule as in one of the atoms. For example, there are two rigorously non-bonding orbitals that are occupied in the ground state of the hydrogen fluoride diatomic molecule; these molecular orbitals are localized on the fluorine atom and are composed of p-type atomic orbital
Atomic orbital
An atomic orbital is a mathematical function that describes the wave-like behavior of either one electron or a pair of electrons in an atom. This function can be used to calculate the probability of finding any electron of an atom in any specific region around the atom's nucleus...
s whose orientation is perpendicular to the internuclear axis. They are therefore unable to overlap and interact with the s-type valence orbital on the hydrogen atom.
Although non-bonding orbitals are often similar to the atomic orbitals of their constituent atom, they do not need to be similar. An example of a non-similar one is the non-bonding orbital of the allyl
Allyl
An allyl group is a substituent with the structural formula H2C=CH-CH2R, where R is the connection to the rest of the molecule. It is made up of a methylene , attached to a vinyl group . The name is derived from the Latin word for garlic, Allium sativum. Theodor Wertheim isolated an allyl...
anion, whose electron density is concentrated on the first and third carbon atoms.
See also
- Molecular orbital theoryMolecular orbital theoryIn chemistry, molecular orbital theory is a method for determining molecular structure in which electrons are not assigned to individual bonds between atoms, but are treated as moving under the influence of the nuclei in the whole molecule...
- Bonding orbital
- Antibonding orbital
- LCAO