Bent's rule describes and explains the relationship between the orbital hybridisations of central

atoms in molecules and the electronegativities ofsubstituents. The rule was stated by Henry
Bent as follows: "Atomic s character concentrates in orbitals directed toward electropositive
substituents".]

The chemical structure of a molecule is intimately related to its properties and

reactivity. Valence bond theory proposes that molecular structures are due to covalent
bonds between

the atoms and

that

each

bond

consists

of

two

overlapping

and

typically hybridised atomic orbitals. Traditionally, p-block elements in molecules are assumed
to hybridise strictly as spn, where n is either 1, 2, or 3. In addition, the hybrid orbitals are all
assumed to be equivalent (i.e. the

n+1 spn orbitals have the same p character). Results from

this approach are usually good, but they can be improved upon by allowing hybridised orbitals
with noninteger and unequal p character. Bent's rule provides a qualitative estimate as to how
these hybridised orbitals should be constructed. [3] Bent's rule is that in a molecule, a central
atom bonded to multiple groups will hybridise so that orbitals with more s character are directed
towards electropositive groups, while orbitals with more p character will be directed towards
groups that are more electronegative. By removing the assumption that all hybrid orbitals are
equivalent spn orbitals, better predictions and explanations of properties such as molecular
geometry and bond strength can be obtained.
Bent's rule can be generalized to d-block elements as well. The hybridisation of a metal center
is arranged so that orbitals with more s character are directed towards ligands that form bonds
with more covalent character. Equivalently, orbitals with more d character are directed towards
groups that form bonds of greater ionic character.[1]
Bond angles[edit]
Knowing the angles between bonds is a crucial component in determining a molecular
structure. In valence bond theory, covalent bonds are assumed to consist of two electrons
lying in overlapping, usually hybridised, atomic orbitals from bonding atoms. Orbital
hybridisation explains why methane is tetrahedral and ethylene is planar for instance.
However, there are deviations from the ideal geometries of sp n hybridisation such as
in water and ammonia. The bond angles in those molecules are 104.5 and 107 respectively,
which are below the expected tetrahedral angle of 109.5. The traditional approach to explain
those differences is VSEPR theory. In that framework, valence electrons are assumed to lie in
hybridised orbitals like other substituents and are assumed to repel each other to a greater
extent than other groups. Although the results and explanation are satisfactory at first glance,
VSEPR theory has been attacked for not having a strong theoretical basis. [1] In particular there

is no computational or theoretical evidence that hybridised orbitals containing lone pairs repel
each other in the way VSEPR theory predicts.
Bents rule provides an alternative explanation as to why some bond angles differ from the
ideal geometry. First, a trend between central atom hybridisation and bond angle can be
determined by using the model compounds methane, ethylene, and acetylene. In order, the
carbon atoms are directing sp3, sp2, and sp orbitals towards the hydrogen substituents. The
bond angles between substituents are 109.5, ~120, and 180. This simple system
demonstrates that hybridised atomic orbitals with higher p character will have a smaller angle
between them. This result can be made rigorous and quantitative as Coulson's theorem (see
Formal theory section below).

Now that the connection between hybridisation and bond angles has been made, Bents rule
can be applied to specific examples. The following were used in Bents original paper. [2]
Molecule

Dimethyl ether

Bond angle between substituents

111

107-109
Methanol

Water

104.5

103.8

Oxygen difluoride
As one moves down the table, the substituents become more electronegative and the bond
angle between them decreases. According to Bent's rule, as the substituent electronegativies
increase, orbitals of greater p character will be directed towards those groups. By the above
discussion, this will decrease the bond angle. This agrees with the experimental results.
Comparing this explanation with VSEPR theory, VSEPR cannot explain why the angle
in dimethyl ether is greater than 109.5 or why the bond angles continue to decrease as the
substituents change.
In predicting the bond angle of water, Bents rule suggests that hybrid orbitals with more s
character should be directed towards the very electropositive lone pairs, while that leaves
orbitals with more p character directed towards the hydrogens. This increased p character in
those orbitals decreases the bond angle between them to less than the tetrahedral 109.5.
The same logic can be applied to ammonia, the other canonical example of this phenomenon.
Bond lengths[edit]
Similarly to bond angles, the hybridisation of an atom can be related to the lengths of the
bonds it forms.[2]
Molecule

Average carboncarbon bond length

1.54

1.50

1.46

The above demonstrates that as bonding orbitals increase in s character, the bond length
decreases. By adding electronegative substituents and changing the hybridisation of the
central atoms, bond lengths can be manipulated.
Molecule

Average carbonfluorine bond length

1.388
Fluoromethane

1.358
Difluoromethane

1.329
Trifluoromethane

1.323
Tetrafluoromethane
Because fluorine is so much more electronegative than hydrogen, in fluoromethane the
carbon will direct a hybrid orbital very high in p character towards the fluorine and orbitals very
high in s character towards the hydrogens. In difluoromethane, the p character now must be
divided amongst both fluorines, decreasing the amount of p character in the hybrid orbitals
relative to fluoromethane. This trend holds all the way to tetrafluoromethane and the increased
s character in the C-F bonds leads to the shorter bond lengths.