Types of Hybridization

There are different types of hybridization depending upon the type of orbitals involved
in mixing such as sp3, sp2, sp, sp3d, sp3d2 etc. Let us discuss various types of
hybridization along with some examples.

Sp3 HYBRIDIZATION
The type of hybridization involves the mixing of one orbital of s sub shell and three
orbitals of p sub shell of the .valence shell to form four sp3 hybrid orbitals of equivalent
energies and shape. Each sp3 hybrid orbital has 25% s-character and 75% p-character.
These hybridized orbitals tend to lie as far apart in space as possible so that the
repulsive interaction between them is minimum. The four sp3 hybrid orbitals are
directed towards the four corners of a tetrahedron. The angle between the sp3 hybrid
orbitals is 109.5° Figure 1.

Fig.1. Tetrahedral orientation of sp3 hybrid orbitals

sp3 hybridization is also known as tetrahedral hybridization. The molecules in which

central atom is sp3 hybridized and is linked to four other atoms directly have
tetrahedral shape.
Formation of methane (CH4) in methane carbon atom acquires sp3 hybrid state as
described below:
Here, one orbital of 2s sub shell and three orbitals of 2p sub shell of excited carbon
atom undergo hybridization to form four sp3 hybrid orbitals. The process involving
promotion of 2s-electron followed by hybridization is shown in Figure 2.
Fig. 2. sp3 hybridization of carbon.

As pointed out earlier the sp3 hybrid orbitals of carbon atom are directed towards the
comers of regular tetrahedron. Each of the sp3 hybrid orbital overlaps axially with half
filled Is-orbital of hydrogen atom constituting a sigma bond Figure3.

Fig. 3. Orbital picture of methane.

Formation of ammonia (NH)3 molecule in NH3 molecule the nitrogen atom adopts sp3-
hybrid state. Three of sp3-hybrid orbitals of the N atom are used for forming sp3-s
(sigma) bonds with three H atoms. The fourth sp3-hybrid orbital carries lone pair of
electrons. The relatively larger lone pair bond pair interactions causes HNH angle to
decrease from 109°.281 to 107°. The ground state, hybrid state of N atom and orbital
overlap are shown in Figure 4.
Fig. 4. Formation of NH3 molecule.

Formation of water (H2O) molecule in H2O molecule, oxygen atom adopts sp3 hybrid
state. Two of the sp3 hybrid orbitals of oxygen contain lone pairs of electrons whereas
the other two hybrid orbitals constitute sp3-(sigma) bonds with H atoms. The lone pair
orbitals exert relatively greater repulsive interactions on bond pair-orbitals causing
HOH angle to decrease from 109°.28′ to 104.5°. The hybridization of O atom along with
orbital overlap in H2Omolecule is shown in Figure 5.

Fig. 5. Formation of H2O molecule

sp2 HYBRIDIZATION
This type of hybridization involves the mixing of one orbital of s sub shell and two
orbitals of p sub shell of the valence shell to form three sp2 hybrid orbitals. These
sp2 hybrid orbitals lie in a plane and are directed towards the corners of an equilateral
triangle Figure 6.

Fig. 6. Trigonal planar orientation of sp2 hybrid orbitals

Each sp2 hybrid orbital has one third s-character and two third p-character.
sp2 hybridization is also called trigonal hybridization. The molecules in which central
atom is sp2 hybridized and is linked to three other atoms directly have triangular planar
shape.
Formation of boron trichloride (BCl3) Boron atom has ground state configuration as ls2,
2s2, 2p1 but in the excited state its configuration is ls2, 2s1, 2px1, 2py1. One 2s-orbital
of boron intermixes with two 2p-orbitals of excited boron atom to form three sp2
hybrid orbitals as shown in Fig. 7.

Fig. 7. sp2 hybrid state of boron.

The sp2 hybrid orbitals of boron are directed towards the corners of an equilateral
triangle and lie in a plane. Each of the sp2 hybrid orbital of boron overlaps axially with
3p-half filled orbital of chlorine atom to form three B-Cl sigma bonds as shown in Fig.
8.
Fig. 8. Orbital diagram of BCI3

sp HYBRIDIZATION
This type of hybridization involves the mixing of one orbital of s sub shell and one
orbital of p sub shell of the atom to form two sp-hybridized orbitals of equivalent
shapes and energies. These sp hybridized orbitals are oriented in space at an angle of
180° Figure 9. This hybridization is also called diagonal hybridization. Each sp hybrid
orbital has equal s and p character, i.e., 50% s-character and 50% p-character. The
molecules in which the central atom is sp hybridized and is linked to two other atoms
directly have linear shape.

Fig. 9. Formation of sp hybrid orbitals

Formation of beryllium fluoride (BeCl2) Beryllium atom has a ground state configuration
as ls2, 2s2. In the excited state one of the 2s electron is promoted to 2p orbitals. One 2s
orbital and one 2p orbital of excited beryllium atom undergo sp hybridization to form
two sp hybridized orbitals as described in Figure 10.
Fig. 10. sp hybrid state of Be

The two sp hybrid orbitals are linear and oriented in opposite directions at an angle of
180°. Each of the sp-hybridized orbitals overlaps axially with 3p half filled orbital of
chlorine atom to form two Be-Cl sigma bonds as shown below:

HYBRIDIZATION INVOLVING d ORBITALS:

The participation of d orbitals in hybridization scheme can take place when d orbitals
are lying vacant or partly filled. s and p orbitals of the outer most shell can use d
orbitals of the outer shell as well as d orbitals of the lower shell for hybridization
depending upon the nature of molecule. For example, 3d orbitals can be involved in
hybridization with 3s, 3p orbitals and also with 4s and 4p-orbital. It is because of the
fact that the energy of 3d orbitals is comparable to 3s and 3p orbitals and also to s and
p orbitals of 4th shell. The important hybridization schemes of s, p, d orbitals are
summarised below in tabular form:
sp3d-HYBRIDIZATION
This type of hybridization involves mixing of one s, three p and one d orbitals to form
five sp3d hybridized orbitals which adopt trigonal bipyramidal geometry as shown in
Figure 12. Three of the hybrid orbitals lie in horizontal plane at angle of 120° to one
another. These are called equatorial orbitals (marked as e). The other two hybrid
orbitals, lie in vertical plane at right angle to the plane of equatorial orbitals and are
called axial orbitals (marked as a).

Fig. 12. Formation of five sp3d hybrid orbitals

Formation of PC15 The ground state electronic configuration of phosphorus is

ls2 2s2 2p6 3s2 3p3 under the conditions of bond formation the 3s electrons get
unpaired and one of the electron is promoted to vacant 3d orbital. The ground state
and excited state configurations of phosphorus are shown in Figure 13.
Fig. 13. Ground state and excited state configuration of phosphorus

Now the five orbitals, one (3s), three (3p) and one (3d) which are half-filled are
hybridized to yield a new set of five sp3d hybrid orbitals, which point towards the five
corners of a trigonal bipyramid Figure 14.

Fig. 14. Trigonal bipyramidal geometry of PCI5 molecule

During the formation of PC15, each of the five sp3d hybrid orbitals overlap axially with
the half-filled 3p orbital of Cl atom to form five P-Cl sigma bonds. Three of the five P-
Cl bonds lie in one plane at an angle of 120° to one another. These are called equatorial
bonds. The other two P-Cl bonds are at right angle to the plane of equatorial bonds,
i.e., one above and other below the plane. These are called axial bonds. As the axial
bond pairs suffer more repulsive interaction from the equatorial bond pairs, therefore,
axial P-CI bonds become slightly longer (219 pm) than the equatorial bonds (204 pm).
The unequal length of axial and equatorial P-Cl bonds in PCl5 has been confirmed by X-
ray diffraction technique. This causes axial bonds to become slightly weaker than the
equatorial bonds, which makes PC15 molecule more reactive.

sp3d2 HYBRIDIZA TION

In this type of hybridization one s, three p and two d orbitals undergo intermixing to
form six identical sp3 d2 hybrid orbitals. These six orbitals are directed towards the
corners of an octahedron and lie in space at an angle of 90° to one another as shown in
Figure 15.
Fig. 15. Formation of six sp3d2 hybrid orbitals

Formation of SF6 The ground state outer shell configuration of Sulphur is 3s23p4. In the
excited state the electron pairs in 3s and 3px orbitals get unpaired and one out of each
pair is promoted to vacant 3dz2 and 3dx2-y2 orbitals. The ground state and excited state
configurations of Sulphur are given as follows:

Now, six orbitals; one (3s), three (3p) and two (3d) orbitals which are half-filled are
hybridized to form six new sp3d2 hybrid orbitals which are projected towards the six
corners of a regular octahedron as shown in Figure 16.

Fig. 16. Octahedral geometry of SF6.

During the formation of SF6, these six sp3 d2 hybrid orbitals overlap with half-filled
orbitals of fluorine atoms to form six S-F sigma bonds. All the six S-F bonds in
SF 6 have same bond length.