Bent Rule and Energetics of Hybridization

From DRGP DREAM DOT

Hybridisation is the concept of mixing atomic orbitals into new hybrid orbitals with different
energies, shapes, etc. than the component atomic orbitals. When a set of hybrid orbital is
constructed by a linear combination of atomic orbitals, the energy of the resulting hybrids is a
weighted average of the energies of the participating atomic orbitals. This energy of
hybridization is of the order of magnitude of bond energies and can thus be important in
determining the structure of molecules. Bent rule encompasses the relationships between
bond polarity (ligand electronegativity) and central -atom geometry through their mutual
connection to central-atom hybridization.

Bent Rule and Energetics of Hybridization

According to hybridisation atomic orbitals combine and redistribute their energies to form
hybrid orbital. These are identical with respect to energy, shape etc. Shapes of the hybrid
orbital depends upon contribution of s, p orbitals and its affect the energy of hybridisation.
Bents rule states that, Atomic s character tends to concentrate in orbitals that are directed
toward electropositive groups and atomic p character tends to concentrate in orbitals that are
directed toward electronegative groups.
1. s orbitals has low energy than p orbital.
2. More s character decrease the energy of bonding orbitals and hence they have shaped
more like a s orbital. More p character increase the energy of bonding orbitals and
hence they have shaped more like a p orbitals.
3. s orbitals are closer to the nucleus, so it stabilize the lone pair. Due to more s character
less repulsion and less hybridisation energy and less bond angle. Vice versa is true for
more p character.
4. The most stable arrangement would be to utilize pure p orbitals for bonding and
letting the lone pair into the pure s orbital.
5. s-Orbitals are more penetrating and electron density is less available for bonding.
Thus, more electronegative atoms would be able to withdraw more electron density
from p orbitals than from s orbitals.
we can also describe bent rule as More electronegative substituents prefer hybrid orbitals
having less s-character and more eletropositive substituents prefer hybrid orbitals having
more s-character.

Exaamples of Bent Rule and Energetics of Hybridization

1. sp3d Hybridisation in PClxF5-x : In sp3d Hybridisation one s, three p and one d-orbitals
form 5 sp3d hybridised orbital. All these five hybrid orbitals are not of the same type so they
can be divided into two non-equivalent sets. The first set is known as equatorial set of
orbitals. It is formed from one s, one px and one py orbitals. The second set is known as axial
set. It is formed from one pz and one d orbitals. It is experimentally observed that the more
electronegative substituent occupies the axial position (as it has less s character)that is f and
less electronegative substituents is equitorially situated that is cl.

2. Less bond angle in CH2F2 : In the case of sp3 hybrididsation, CH4 or CCl4 formed
tetrahedral geometry with bond angle 109.5o. But in the case of CH2F2, the F-C-F bond angle
is less, this explained on the basis of Bents rule. F is more electronegative than H so F-C-F scharacter is less than 25% while in H-C-H it is more than 25%. Due to less s-character bond
angle is less in CH2F2.

In chemistry, Bent's rule describes and explains the relationship between the orbital
hybridization of central atoms in molecules and the electronegativities of substituents.[1][2] The
rule was stated by Henry Bent as follows: "Atomic s character concentrates in orbitals
directed toward electropositive substituents".[2]
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 isovalent hybridization, in which the
hybridised orbitals may have 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]
Contents

1 History

2 Justification

3 Examples

3.1 Bond angles

3.2 Bond lengths

3.3 JCH Coupling constants

3.4 Inductive effect

4 Formal theory

5 See also

6 References

History

In the early 1930s, shortly after much of the initial development of quantum mechanics, those
theories began to be applied towards molecular structure by Pauling,[4] Slater,[5] Coulson,[6]
and others. In particular, Pauling introduced the concept of hybridisation, where atomic s and
p orbitals are combined to give hybrid sp, sp2, and sp3 orbitals. Hybrid orbitals proved
powerful in explaining the molecular geometries of simple molecules like methane
(tetrahedral with an sp3 carbon). However, slight deviations from these ideal geometries
became apparent in the 1940s.[7] A particularly well known example is water, where the angle
between hydrogens is 104.5, far less than the expected 109.5. To explain such
discrepancies, it was proposed that hybridisation can result in orbitals with unequal s and p
character. A. D. Walsh described in 1947[7] a relationship between the electronegativity of
groups bonded to carbon and the hybridisation of said carbon. Finally, in 1961, Henry A.
Bent published a major review of the literature that related molecular structure, central atom
hybridisation, and substituent electronegativities [2] and it is for this work that Bent's rule
takes its name.
Justification

Structure of fluoromethane. The C-H and C-F bonds are polar and so the electron
density will be shifted towards carbon in the C-H bonds and towards fluorine in
the C-F bonds. Directing orbitals with more s character towards the hydrogens is
stabilizing, while directing orbitals of less s character towards the fluorine is
destabilizing but to a lesser extent.

An informal justification of Bent's rule relies on s orbitals being lower in energy than p
orbitals.[2] Bonds between elements of different electronegativities will be polar and the
electron density in such bonds will be shifted towards the more electronegative element.
Applying this to the molecule fluoromethane provides a demonstration of Bent's rule.

Because carbon is more electronegative than hydrogen, the electron density in the C-H bonds
will be closer to carbon. The energy of those electrons will depend heavily on the hybrid
orbitals that carbon contributes to these bonds because of the increased electron density near
the carbon. By increasing the amount of s character in those hybrid orbitals, the energy of
those electrons can be reduced because s orbitals are lower in energy than p orbitals.
By the same logic and the fact that fluorine is more electronegative than carbon, the electron
density in the C-F bond will be closer to fluorine. The hybrid orbital that carbon contributes
to the C-F bond will have relatively less electron density in it than in the C-H case and so the
energy of that bond will be less dependent on the carbon's hybridisation. By directing hybrid
orbitals of more p character towards the fluorine, the energy of that bond is not increased very
much.
Instead of directing equivalent sp3 orbitals towards all four substituents, shifting s character
towards the C-H bonds will stabilize those bonds greatly because of the increased electron
density near the carbon, while shifting s character away from the C-F bond will increase its
energy by a lesser amount because that bond's electron density is further from the carbon. The
atomic s character on the carbon atom has been directed toward the more electropositive
hydrogen substituents and away from the electronegative fluorine, which is exactly what
Bent's rule suggests.
Although fluoromethane is a special case, the above argument can be applied to any structure
with a central atom and 2 or more substituents. The key is that concentrating atomic s
character in orbitals directed towards electropositive substituents is more favorable than
removing s character from orbitals directed towards electronegative substituents.
Examples

Bents rule can be used to explain trends in both molecular structure and reactivity. After
determining how the hybridisation of the central atom should affect a particular property, the
electronegativity of substituents can be examined to see if Bents rule holds.
Bond angles

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 spn 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
localized regions and lone pairs are assumed to repel each other to a greater extent than
bonding pairs.

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, which
considers the group electronegativity of the methyl group to be less than that of the hydrogen
atom because methyl substitution reduces the acid dissociation constants of formic acid and
of acetic acid.[2]
Molecule

Bond angle between substituents

111
Dimethyl ether

107-109
Methanol

104.5
Water

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
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

Similarly to bond angles, the hybridisation of an atom can be related to the lengths of the
bonds it forms.[2] As bonding orbitals increase in s character, the bond length decreases.
Molecule

Average carboncarbon bond length

1.54

1.50

1.46

By adding electronegative substituents and changing the hybridisation of the central atoms,
bond lengths can be manipulated. If a molecule contains a structure X-A--Y, replacement of
the substituent X by a more electronegative atom changes the hybridization of central atom A
and shortens the adjacent A--Y bond.
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 hybrid orbitals higher in s character towards the three hydrogens than
towards the fluorine. In difluoromethane, there are only two hydrogens so less s character in
total is directed towards them and more is directed towards the two fluorines, which shortens
the CF bond lengths relative to fluoromethane. This trend holds all the way to
tetrafluoromethane whose C-F bonds have the highest s character (25%) and the shortest
bond lengths in the series.
The same trend also holds for the chlorinated analogs of methane, although the effect is less
dramatic because chlorine is less electronegative than fluorine.[2]
Molecule

Average carbonchlorine bond length

1.783
Chloromethane

1.772
Dichloromethane

1.767
Trichloromethane

1.766
Tetrachloromethane

The above cases seem to demonstrate that the size of the chlorine is less important than its
electronegativity. A prediction based on sterics alone would lead to the opposite trend, as the
large chlorine substituents would be more favorable far apart. As the steric explanation
contradicts the experimental result, Bents rule is likely playing a primary role in structure
determination.
JCH Coupling constants

Perhaps the most direct measurement of s character in a bonding orbital between hydrogen
and carbon is via the 1H13C coupling constants determined from NMR spectra. Theory
predicts that JCH values will be much higher in bonds with more s character.[8][9]
Molecule

JCH (of the methyl protons)

125 Hz

Methane

127 Hz
Acetaldehyde

134 Hz
1,1,1Trichloroethane

141 Hz
Methanol

149 Hz
Fluoromethane

As the electronegativity of the substituent increases, the amount of p character directed

towards the substituent increases as well. This leaves more s character in the bonds to the
methyl protons, which leads to increased JCH coupling constants.
Inductive effect

The inductive effect can be explained with Bents rule.[10] The inductive effect is the
transmission of charge through covalent bonds and Bents rule provides a mechanism for
such results via differences in hybridisation. In the table below,[11] as the groups bonded to the
central carbon become more electronegative, the central carbon becomes more electronwithdrawing as measured by the polar substituent constant. The polar substituent constants
are similar in principle to values from the Hammett equation, as an increasing value
corresponds to a greater electron-withdrawing ability. Bent's rule suggests that as the
electronegativity of the groups increase, more p character is diverted towards those groups,
which leaves more s character in the bond between the central carbon and the R group. As s
orbitals have greater electron density closer to the nucleus than p orbitals, the electron density
in the CR bond will more shift towards the carbon as the s character increases. This will
make the central carbon more electron-withdrawing to the R group.[7] Thus, the electronwithdrawing ability of the substituents has been transferred to the adjacent carbon, exactly
what the inductive effect predicts.

Substituent

Polar substituent constant

(larger values imply greater
electron-withdrawing ability)

-0.30
tButyl

0.00
Methyl

1.05
Chloromethyl

1.94
Dichloromethyl

2.65
Trichloromethyl
Formal theory

Bent's rule provides an additional level of accuracy to valence bond theory. Valence bond
theory proposes that covalent bonds consist of two electrons lying in overlapping, usually
hybridised, atomic orbitals from two bonding atoms. The assumption that a covalent bond is a
linear combination of atomic orbitals of just the two bonding atoms is an approximation (see
molecular orbital theory), but valence bond theory is accurate enough that it has had and
continues to have a major impact on how bonding is understood.[1]
In valence bond theory, two atoms each contribute an atomic orbital and the electrons in the
orbital overlap form a covalent bond. Atoms do not usually contribute a pure hydrogen-like

orbital to bonds.[4] If atoms could only contribute hydrogen-like orbitals, then the
experimentally confirmed tetrahedral structure of methane would not be possible as the 2s
and 2p orbitals of carbon do not have that geometry. That and other contradictions led to the
proposing of orbital hybridisation. In that framework, atomic orbitals are allowed to mix to
produce an equivalent number of orbitals of differing shapes and energies. In the
aforementioned case of methane, the 2s and three 2p orbitals of carbon are hybridized to yield
four equivalent sp3 orbitals, which resolves the structure discrepancy. Orbital hybridisation
allowed valence bond theory to successfully explain the geometry and properties of a vast
number of molecules.
In traditional hybridisation theory, the hybrid orbitals are all equivalent.[12] Namely the atomic
s and p orbital(s) are combined to give four spi3 = 1 4 (s+ 3pi) orbitals, three spi2 = 1 3 (s+
2pi) orbitals, or two spi = 1 2 (s+ pi) orbitals. These combinations are chosen to satisfy two
conditions. First, the total amount of s and p orbital contributions must be equivalent before
and after hybridisation. Second, the hybrid orbitals must be orthogonal to each other.[12] If two
hybrid orbitals were not orthogonal, by definition they would have nonzero orbital overlap.
Electrons in those orbitals would interact and if one of those orbitals were involved in a
covalent bond, the other orbital would also have a nonzero interaction with that bond,
violating the two electron per bond tenet of valence bond theory.
To construct hybrid s and p orbitals, let the first hybrid orbital be given by s+i pi, where pi
is directed towards a bonding group and i determines the amount of p character this hybrid
orbital has. This is a weighted sum of the wavefunctions. Now choose a second hybrid orbital
s+j pj, where pj is directed in some way and j is the amount of p character in this second
orbital. The value of j and direction of pj must be determined so that the resulting orbital can
be normalized and so that it is orthogonal to the first hybrid orbital. The hybrid can certainly
be normalized, as it is the sum of two normalized wavefunctions. Orthogonality must be
established so that the two hybrid orbitals can be involved in separate covalent bonds. The
inner product of orthogonal orbitals must be zero and computing the inner product of the
constructed hybrids gives the following calculation.
Note that the s orbital is normalized and so the inner product . Also, the s orbital is orthogonal
to the pi and pj orbitals, which leads to two terms in the above equaling zero. Finally, the last
term is the inner product of two normalized functions that are at an angle of ij to each other,
which gives cos ij by definition. However, the orthogonality of bonding orbitals demands
that , so we get Coulson's Theorem as a result:[12]
This means that the four s and p atomic orbitals can be hybridised in arbitrary directions
provided that all of the coefficients satisfy the above condition pairwise to guarantee the
resulting orbitals are orthogonal.
Bent's rule, that centrals atoms direct orbitals of greater p character towards more
electronegative substituents, is easily applicable to the above by noting that an increase in the
i coefficient increases the p character of the s + i pi hybrid orbital. Thus, if a central atom A

is bonded to two groups X and Y and Y is more electronegative than X, then A will hybridise
so that X < Y. More sophisticated theoretical and computation techniques beyond Bents rule
are needed to accurately predict molecular geometries from first principles, but Bents rule
provides an excellent heuristic in explaining molecular structures.

Limitation of CFT
1. The CFT ignores the attractive forces between the d- electrons of the metal ion and
nuclear charge on the ligand atom. Therefore all properties are dependent upon the
ligand orbital and their interactions with metal orbitals are not explained.
2. In CFT model partial covalencey of metal-ligand bonds are not taken into
consideration. According to CFT metal ligands bonding is purely electrostatic.
Which is not so true.
3. In CFT only d- electrons of the metal ion are considerd the other orbitals such as s, p x,
py, pz are not taken into consideration.
4. In CFT orbitals of ligand are not considerd.
5. CFT mainly affected by spectra chemical series , which is as below:
I < Br < Cl < F < OH < H2O < NH3 < CO etc.
1. As a ligand are assumed to be point charges, it is expected that the ionic ligand
should have greater splitting effect. However actually they found to be at
lower end of the spectrochemical series.
2. Though OH in the spectrochemical series lies below H2O and NH3 , yet it
produces greater splitting effect.
3. CFT is unable to explain the relative strength of ligands.
6. CFT gave no information about bond formation in ligand.
7. CFT dont explain the effect of bond on 0.