GT and Hybridization (S2)

APPLICATIONS OF GROUP THEORY
Lecture notes: Dr. Cyriac Mathew Lecture notes
Determination of the type of hybridization:
Hybridization is a concept put forward to explain the shapes of molecules. The basic
assumption in this concept is that the central atom in a molecule is not using pure atomic orbitals for
bonding; but the various types of the orbitals of this atom undergo mixing up forming a set of
equivalent orbitals with definite directional properties and these orbitals can form stronger bonds.
Lecture notes: Dr. Cyriac Mathew
We usually ascribe shapes of molecule to one or another type of hybridization. We can apply group
theory to find out the various types of orbitals involved in hybridization provided the shape of the
molecule is known. The shape of the molecule will be decided by the directions of the hybrid orbitals
around the central atom. For example, a tetrahedral molecule will be formed by a central atom which
has undergone tetrahedral hybridization.
To identify the various atomic orbitals undergoing hybridization, first we have

to identify the point group of the molecule. This will give an idea about the distribution of various
pendent atoms around the central atom. The hybrid orbitals will be directed towards the pendent
atoms. Thus, the point groups of the molecule will tell us in what direction the hybrid orbitals are
distributed. These hybrid orbitals will be taken as the base vectors to evaluate the total character,
which will then be reduced to find out the various irreducible representations which add up to the
total character. It follows that the hybrid orbitals are transforming as these irreducible
representations. We can find out the atomic orbitals which transform according to these irreducible
representations. A set of hybrid orbitals of a particular symmetry can be formed only from a set
Lectrue notes Dr. Cyriac Mathew
of atomic orbitals of the same symmetry. Hence the atomic orbitals which transform according to
these irreducible representations will be mixing up to give the hybrid orbitals.
Hybridization scheme in sigma bonding – tetrahedral hybridization.
Let us first identify the atomic orbitals involved in tetrahedral hybridization. A tetrahedral molecule
Lecture notes : Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew
belongs to Td point group. The hybrid orbitals are, therefore, directed towards the corners of a regular
tetrahedron. We shall denote these vectors r1, r2, r3 and r4 as shown below. Now we find out the characters for
E, C3, C2, S4 and d taking these vectors as the basis.
Methane
The total character in an operation is equal to the number of vectors retaining position since only these
vectors contribute to the character. The vectors which are shifted do not contribute to the character because
the corresponding coefficients do not fall along the diagonal.
For the identity operation, all the vectors retain position and
r1
hence its character will be equal to the total number of vectors in
question. In the tetrahedral hybridization, it is 4. For other
operations, the number of vectors unshifted will be equal to those
through which the corresponding symmetry element passes. Thus,
each of the C3 axes passes through one vector only. Hence the
character of the C3 operation is 1. The C2 axes pass through none of r2 r4
the vectors and their character is zero. The S4 also passes through
r3
none of the vectors and their character is zero. Each of the
Direction of  bonds in tetrahedral molecules
d passes through two of the vectors and the character of d is
therefore 2. The character table for Td point group along with the total characters for methane is given below.
1
𝑇𝑑 𝐸 8𝐶3 3𝐶2 6𝑆4 6𝜎𝑑
𝐴1 1 1 1 1 1 𝑥2 + 𝑦2 + 𝑧2
𝐴2 1 1 1 −1 −1
𝐸 2 −1 2 0 0 (𝑅𝑥 , 𝑅𝑦 , 𝑅𝑧 ) (2𝑧 2 − 𝑥 2 − 𝑦 2 , 𝑥 2 − 𝑦 2 )
𝑇1 3 0 −1 1 −1
𝑇2 3 0 −1 −1 1 (𝑥, 𝑦, 𝑧) (𝑥𝑧, 𝑦𝑧, 𝑥𝑦)
𝛤𝜎 4 1 0 0 2
A comparison of  and the irreducible representations of the character table shows that  is not an irreducible
representation. Hence it is reducible, and we shall reduce it using the reduction formula,
1
ni =
h
 g( R ) i ( R )  ( R )
ni = the number of times the ith irreducible representation occurring in the reducible representation
h = the order of the group

i(R) =the character of the operation R in the ith irreducible representation
(R) = the corresponding character in the reducible representation (total character)
g(R) = the number of conjugate elements occurring in the class of the element R.
nA1 = 1
24 1.1.4 + 8.1.1 + 3.1.0 + 6.1.0 + 6.1.2 = 1
nA2 = 1
24 1.1.4 + 8.1.1 + 3.1.0 + 6. − 1.0 + 6.(−1).2
R
= 0
nE = 1
24 1.2.4 + 8.(−1).1 + 3.2.0 + 6.0.0 + 6.0.2
R
= 0
1.3.4 + 8.0.1 + 3.(−1).0 + 6.1.0 + 6.(−1).2

nT1 = 1 = 0
24
R
nT2 = 1
24 1.3.4 + 8.0.1 + 3.(−1).0 + 6.(−1).0 + 6.1.2
R
= 1
Thus, our reducible representation  contains the irreducible representations, A1 and T2.
Or, 𝛤𝜎  A1 + T2.
This means that one of the hybrid orbitals has a1 (small letter for orbitals) symmetry and the other
three have t2 symmetry. 𝛤𝜎 means we have only sigma molecular orbitals. The hybrid orbitals of these
symmetries can be formed only from atomic orbitals of the same symmetries. The atomic orbitals having these
symmetries can be identified from the character table.
Since the s-orbitals are totally symmetric, they will be transforming as the totally symmetric
representation in all groups. In the T d point group, therefore, s-orbitals transform as a1 species.
The px, py and pz -orbitals as well as the dxy, dxz and dyz -orbitals transform as t2 species. This
may be listed as follows:
Symmetry species a1 t2
Atomic orbitals coming under each symmetry s
px, py,pz
dxy, dxz, dyz
The s-orbital must involve in the hybridization since there should be one orbital
of symmetry a1. As t2 indicates a triply degenerate set of orbitals, either the p x, py pz-orbitals
or the set of dxy, dxz, dyz -orbitals may involve in hybridization. Hence, a set of four tetrahedral
hybrid orbitals may be formed from one s- and three p-orbitals or one s- and three d-orbitals.
Group theory can tell us only which orbitals are involved in a particular type of
hybridization. It cannot give any idea regarding the energy of orbitals involved. We have to get
this idea from quantum mechanics. From energy considerations, we can say
2
that the s- and p-orbitals utilized for tetrahedral hybridization will be from the same main energy level and
hence we denote the hybridization by sp 3. However, the s- and d-orbitals for the
tetrahedral hybridization cannot be from the same main shell since there will be an appreciable
difference between the energies of s and d-orbitals of the same shell. Moreover, there will be a
set of three p-orbitals in between the s- and d-orbitals. But the energies of the ns-orbital and the
(n−1) d-orbitals will be comparable and hence they can undergo hybridization. This will be
denoted by d3s. Thus, tetrahedral hybridization can be sp3 or d3s. In some cases, there may be an
appropriate mixing among the p and d-orbitals.
For the elements of the second period, the tetrahedral hybridization (as in CH 4 or NH4+) will be
sp3 as d-orbitals are available only in the upper energy levels. In MnO4− and CrO42−, the
type of hybridization is most probably d 3s, in which 3d-and 4s-orbitals are used. Of course, we
do not discard completely the possibility of some mixing among 3d and 4p-orbitals.
PROJECTION OPERATORS AND CONSTRUCTION OF SALCs
We know that the wave functions for molecular orbitals are formed by linear
combinations of a set of atomic orbitals. These wave functions satisfy the symmetry requirements
of the molecular system. Therefore, they may be regarded as symmetry adapted linear combinations
(SALCs). The algebraic equations for SALCs can be generated by applying the projection operator
technique. The reducible representation of the basis set is a linear combination of irreducible
representations. Each SALC must have the symmetry of an irreducible representation. To generate
a SALC belonging to one of these irreducible representations, the projection operator for that
particular irreducible representation is applied to one function in the basis set.
Suppose our aim is to find the allowed SALCs from a set of functions 1 , 2 ,......, n ,which
form the basis for a reducible representation of the group. For this purpose, the basis-functions must
be related to each other by the operators of the group. That is, when an operation of the group is
carried out on a function, it should change into itself or other functions in the set. To construct
the SALC associated with the ith irreducible representation, Si, one may apply the projection
operator Pˆi to any one of the basis-functions  according to the expression,

𝑙
𝑆𝑖 = 𝑃̂𝑖 𝜙 = 𝑖 ∑𝑅 𝜒𝑖 (𝑅)𝑅̂ 𝜙, where li, is the dimension of the ith irreducible representation, h is the order
ℎ
of the group, i(R) is the character of each operation in the ith irreducible representation and R̂ is each of the
operations of the group.
It should be remembered that when we seek to construct hybrid orbitals as LCAOs, we must realize that
the process is actually the inverse. This means that we start with an assumed set of hybrid orbitals obtained
from the shape of the molecule and transform them to the atomic orbitals of the central atom with matching
symmetry. We then take the inverse of this to obtain the actual hybrid orbitals.
This could be further explained in the following manner. We start with the hybrids with their desired
geometrical orientation as our basis set. For e.g., in an AB4 type molecule the four hybrids points toward the
corners of a regular tetrahedron. We then generate a reducible representation and find out the irreducible
representations involved in it. The irreducible representation indicates the symmetries of the various atomic
orbitals that may be combined on the central atom. Here the set of hybrids used is the known quantity and the
atomic orbitals comprising them are the unknowns to be determined. As a result, if we were to apply projection
operators to the hybrids that form the basis set we would obtain expressions for each of the component
conventional atomic orbitals (s, p, d …) as SALCs of various hybrid functions. This is not the result that we need.
What we need is to formulate hybrids in terms of conventional atomic orbitals. Fortunately, from the properties
of matrices if we take the inverse of the transformation matrix for obtaining AOs from hybrids, we will get
hybrids as SALCs of atomic orbitals. Let us take methane as an example.
3
Determination (Quantitative treatment) of hybrid orbitals of AB4 (CH4)
The quantitative expressions for the sp 3 hybridized orbitals

can be written by an examination of the methane molecule being C3(2)
inscribed in a cube. If we think of the central carbon atom as the (-1,-1,1)
origin of coordinates, then the hybrids can be regarded as vector
2
combinations of px, py and pz orbitals. The hybrids have been z (1,1,1) C
3(1)
labelled according to these combinations. Thus, the hybrid labelled 1
(1,1,1) may be interpreted as the combination of unit vectors such

y
as, ipx + jpy + kpz.
4 (-1,1,-1)
The results of applying the symmetry operations of the x C3(4)
point group Td to the hybrid orbitals of carbon atom represented as 3
ψ1, ψ2, ψ3 and ψ4, is given below. Each hybrid orbital consists of
an s orbital spanning (covering) a1, and three p orbitals spanning C3(3) (1,-1,-1)
t2. We list the symmetry operators and their action on any three of Hybrid sp3 orbitals in methane, directional
the hybrid orbitals ψ1 to ψ4 and apply the projection relationship to the cube. Carbon at the centre
operators ̂𝑃𝑎1 and 𝑃̂𝑡2 . We note that 𝑃̂𝑎1 applied to any of the ψ1 to ψ4, leads to the same SALC. Therefore,
only three, say ψ1 to ψ3, are needed to form SALCs with 𝑃̂𝑡 .
2
2 2 2 2
Td E C3(1) C3(1) C3(2) C3(2) C3(3) C3(3) C3(4) C3(4) C2 x C2 y C2 z
ψ1 ψ1 ψ1 ψ1 ψ3 ψ4 ψ4 ψ2 ψ3 ψ2 ψ3 ψ4 ψ2
ψ2 ψ2 ψ4 ψ3 ψ2 ψ2 ψ1 ψ4 ψ1 ψ3 ψ4 ψ3 ψ1
ψ3 ψ3 ψ2 ψ4 ψ1 ψ4 ψ3 ψ3 ψ2 ψ1 ψ1 ψ2 ψ4
S4 x S 43x S4 y S 43y S4 z S 43z 12  34 13  24  23 14

ψ1 ψ4 ψ2 ψ2 ψ3 ψ3 ψ4 ψ1 ψ2 ψ1 ψ3 ψ4 ψ1
ψ2 ψ1 ψ3 ψ4 ψ1 ψ4 ψ3 ψ2 ψ1 ψ4 ψ2 ψ2 ψ3
ψ3 ψ2 ψ4 ψ1 ψ4 ψ2 ψ1 ψ4 ψ4 ψ3 ψ1 ψ3 ψ2
After applying projection operators1 as mentioned above, we get the four conventional atomic orbitals in
terms of four hybrids as follows.
1 1 1 1
𝑠 = 2 𝜓1 + 2 𝜓2 + 2 𝜓3 + 2 𝜓4
1 1 1 1
𝑝𝑥 = 𝜓1 − 𝜓2 + 𝜓3 − 𝜓4
2 2 2 2
1 1 1 1
𝑝𝑦 = 2 𝜓1 − 2 𝜓2 − 2 𝜓3 + 2 𝜓4
1 1 1 1
𝑝𝑧 = 𝜓1 + 𝜓2 − 𝜓3 − 𝜓4
2 2 2 2
Writing these equations as a transformation matrix we get,
𝑠 1⁄ 1⁄ 1⁄ 1⁄ 𝜓1
2 2 2 2
𝑝𝑥 1⁄2 1
− ⁄2 1⁄ − 1⁄2 𝜓2
= 2 ……. (1)
𝑝𝑦 1⁄ − 1⁄2 1
− ⁄2 1⁄ 𝜓
2 2 3
1
[ 𝑝𝑧 ] [ ⁄2 1⁄ − 1⁄2 1
− ⁄2] [𝜓4 ]
2
1See (1) Semester I notes, “Application of group theory – Projection operators and construction of SALCs”, for H2O and
NH3
(2) Refer page 114 “Chemical applications of Group theory” F. A. Cotton, 3 rd edition.
4
Let the 4 × 4 matrix is represented as A. The transformation matrix to obtain hybrid orbitals will be the
inverse of equation (1). Let it be equation (2)
𝜓1 𝑏11 𝑏12 𝑏13 𝑏14 𝑠

𝜓 𝑏 𝑏22 𝑏23 𝑏24 𝑝𝑥
[ 2 ] = [ 21 ] [ ] ……. (2)
𝜓3 𝑏31 𝑏32 𝑏33 𝑏34 𝑝𝑦
𝜓4 𝑏41 𝑏42 𝑏43 𝑏44 𝑝𝑧
Let the 4 × 4 matrix in equation (2) is represented as B. Now we have to find out the element of the B
matrix. However, A and B are orthogonal matrices. This means that the inverse of one is the transpose of the
other. As such, the elements in each successive row of B are elements from each successive column of A
and vice versa. i.e., (𝐵)𝑖𝑗 = 𝑏𝑖𝑗 = 𝑎𝑗𝑖 . Using the transposed numerical coefficients from (1) as 𝑏𝑖𝑗 , we obtain
1⁄ 1⁄ 1⁄ 1⁄ 𝑠
𝜓1
2 2 2 2
𝜓2 1⁄2 1
− ⁄2 1
− ⁄2 1⁄ 𝑝𝑥
= 2 ……(3)
𝜓3 1⁄ 1⁄ − 1⁄2 − 1⁄2 𝑝𝑦
2 2
1
[𝜓4 ] [ ⁄2 1
− ⁄2 1⁄ − 1⁄2] [ 𝑝𝑧 ]
2
Therefore, the individual sp3 hybrid orbitals are,

1
𝜓1 = 2 (𝑠 + 𝑝𝑥 + 𝑝𝑦 + 𝑝𝑧 )
1
𝜓2 = 2 (𝑠 − 𝑝𝑥 − 𝑝𝑦 + 𝑝𝑧 )
1
𝜓3 = 2 (𝑠 + 𝑝𝑥 − 𝑝𝑦 − 𝑝𝑧 )
1
𝜓4 = 2 (𝑠 − 𝑝𝑥 + 𝑝𝑦 − 𝑝𝑧 )
The above procedure can be extended to obtain equations for other sets of equivalent hybrid orbitals.
This is a conventional representation or symmetric way of writing the four sp 3 hybrid orbitals. Here none of
them lie along x, y, or z axis.
AB3 Type Molecules (eg. BF3)
Let us next consider triangular planar AB 3 type molecule. Its point group
is D3h. The directions of the hybrid orbitals which form the basis vectors are r2
shown in the figure. The operations associated with D3h are E, C3, C2, S3, h, and
v. During the operation E, all the three vectors retain position and hence the
character is 3. During C3 all the vectors shift, (C3) = 0. Each of the C2 axes passes
r1
through one of the vectors; hence  (C2) = 1. The S3 axis coincides with the C3,
hence (S3) = 0. As the h passes through all the vectors, (h) = 3. Each v passes
through one vector and so (v) = 1. These characters are tabulated in the
following table along with the character table of D3h. Therefore, the total r3
character is,
𝐷3ℎ 𝐸 2𝐶3 3𝐶2 𝜎ℎ 2𝑆3 3𝜎𝑣
𝛤𝜎 3 0 1 3 0 1
The character table for D3h with the total character (reducible representation) is given below:
5
E 2C3 3C2  h 2S3 3 V
D3h
A1' 1 1 1 1 1 1 x2 + y 2 , z 2
A2' 1 1 −1 1 1 −1 Rz
E' 2 −1 0 2 −1 0 ( x, y ) ( x 2 − y 2 , xy )
A1'' 1 1 1 −1 −1 −1
A2'' 1 1 −1 −1 −1 1 z
2 −1 0 −2 1
E '' 0 ( Rx , Ry ) ( xz, yz )
 3 0 1 3 0 1
We need calculate n(A1’), n(E'), (nA"2) and n(E’’) since A2’ and A1’’ are not associated with any
atomic orbitals. Reduction shows that (columns of C 3 and S3 can be excluded from calculation).  = A1’ + E’. The
hybrid orbitals have symmetries A1’ and E'. Atomic orbitals having these symmetries alone can hybridize to
give the hybrid orbitals. The possible atomic orbitals are listed below.
Symmetry species a1’ e’

Atomic orbitals s p x, p y
d z2 d x2 − y 2 , d xy
The possible combinations are s, px, py (sp2); s, d x2 − y 2 , d xy (d2s); d z , px , p y (p2d); and finally, d z2 , d x2 − y 2 , d xy (d3).
2
All these four hybridizations can give rise to triangular planar molecules belonging to D 3h point group. Which of
these feasible is decided by energy values and orbital availability. Thus, in BF3, BCl3, etc. sp2 hybridization is
most feasible. In the case of transition metals, in species like TiO 32− there is possibility of the involvement of d-
orbitals in triangular planar hybridization.

It is to be specially noted that the p-orbitals used in sp2-hybridization are the px- and py-orbitals.
Due to the directions of the symmetry elements we have fixed, the bonds are lying
in the xy-plane, hence the use of px- and py-orbitals in the hybridization. So also, if d-orbitals are
used in the place of px and py the two d-orbitals, viz. d x2 − y 2 and dxy are in the xy-plane, whereas
the d-orbitals used in the place of the s-orbital is the d z 2 . Group theory can thus tell us which of the p- or d-
orbitals are actually involved in hybridization of a particular type.
Construction of hybrid orbitals
For BF3 molecule sp2 hybridization involving 2s, 2px and 2py is given for the central boron atom. The
three equivalent sp2 hybrid orbitals may be represented as 𝜓1 , 𝜓2 and 𝜓3 . These three hybrid orbitals form
three vectors from the boron atom. Taking the hybrid orbitals as basis set we use the projection operator
𝑙
method. The 𝑖th SALC, 𝑆𝑖 = 𝑃̂𝑖 𝜙 = 𝑖 ∑𝑅 𝜒𝑖 (𝑅)𝑅̂ 𝜙
ℎ
z
where li, is the dimension of the ith irreducible representation, h is the
order of the group, i(R) is the character of each operation in the ith F
irreducible representation and R̂ is each of the operations of the

group. 𝜓2
v B
F
x
Thus, we get the AOs in terms of hybrid orbitals as, 𝜓1
𝜓3
1 1 1
𝑠= 𝜓 + 𝜓 + 𝜓
√ 3 1 √ 3 2 3 3
√
2 1 1
𝑝𝑥 = 𝜓 − 𝜓 − 𝜓3
√6 1 √6 2 √6 F
1 1
𝑝𝑦 = 𝜓2 − 𝜓3
√2 √2
Writing in the transformation matrix form,
6
1 1 1
𝑠
√3 √3 √3
𝜓1
2 1 1
A = [𝑝𝑥 ] = − − [𝜓2 ] ……. (1)
√6 √6 √6
𝑝𝑦 1 1
[0 − 𝜓3
√2 √2]
Let the 3 × 3 matrix is represented as A. The transformation matrix to obtain hybrid orbitals will be the
inverse of equation (1). Let it be equation (2)
𝜓1 𝑏11 𝑏12 𝑏13 𝑠

𝐵 = [𝜓2 ] = [𝑏21 𝑏22 𝑏23 ] [𝑝𝑥 ] …… (2)
𝜓3 𝑏31 𝑏32 𝑏33 𝑝𝑦
Let us denote the 3 × 3 matrix in equation (2) as B. Now we have to find out the element of the B matrix.
However, A and B are orthogonal matrices. This means that the inverse of one is the transpose of the other.
As such, the elements in each successive row of B are elements from each successive column of A and vice
versa. i.e., (𝐵)𝑖𝑗 = 𝑏𝑖𝑗 = 𝑎𝑗𝑖 . Using the transposed numerical coefficients from (1) as 𝑏𝑖𝑗 , we obtain
1 2
𝜓1 0 𝑠
√3 √6
1 1 1
[𝜓2 ] = − [𝑝𝑥 ] ………. (3)
√3 √6 √2
1 1 1 𝑝𝑦
𝜓3 [√3 − −
√6 √2]
Thus the projection operator technique is used to transform a set of equivalent orbitals (these may be
identified with the hybrid orbitals of the central atom B or with the -orbitals of the pendent atoms F) into
symmetry adapted linear combinations. The hybrid orbitals on boron could be written as,
1 2
𝜓1 = 2𝑠 + 2𝑝𝑥
√3 √6
1 1 1
𝜓2 = 2𝑠 − 2𝑝𝑥 + 2𝑝𝑦
√3 √ 6 √2
1 1 1
𝜓3 = 2𝑠 − 2𝑝𝑥 − 2𝑝𝑦
√3 √6 √2
AB5 Type Molecules (eg. PCl5)
The PCl5 molecule, which is trigonal bipyramidal, also belongs to the D3h point group. The elements of
the group are, E, C3, C2, S3, h, and v. The following figure shows the direction of vectors which represent the
hybrid orbitals. The reducible representation for the molecule can be determined in the following way: For the
E operation all the vectors remain unshifted and hence (E) =
5. If we imagine C3 is passing through r4 and r5,
only the three vectors r1, r2, and r3 are shifted during C3
operation. Hence (C3) = 2. Each of the C2 axes pass only r4
through one vector, and hence all other vectors shift position.
Therefore (C2) = 1. r1, r2, and r3 remain unchanged during h r3
and hence (h) = 3. During S3, taking S3 passing through r4 and
r5, all the vectors are shifted. Hence ( S3) = 0. Also, each of the
r2 r1
V planes pass through three vectors and hence (V) = 3.
Therefore, the total reducible representation for PCl 5 molecule r5
D3h E 2C3 3C2  h 2S3 3 V
will be,
 5 2 1 3 0 3
7
The character table for D3h point group when combined with  could be written as;
D3h E 2C3 3C2  h 2S3 3 V

A1' 1 1 1 1 1 1 x2 + y 2 , z 2
A2' 1 1 −1 1 1 −1 Rz
E' 2 −1 0 2 −1 0 ( x, y ) ( x 2 − y 2 , xy )
A1'' 1 1 1 −1 −1 −1
A2'' 1 1 −1 −1 −1 1 z
E '' 2 −1 0 −2 1 0 ( Rx , Ry ) ( xz, yz )
 5 2 1 3 0 3
Applying the reduction formula  is found to be  2A1’ + E’ + A2’’. The various orbitals coming under these
symmetry species are:

Symmetry species 2a1’ e’ a2’’
Atomic orbitals s (px, py) pz
𝑑𝑧 2 (𝑑𝑥 2−𝑦2 , 𝑑𝑥𝑦 )
Since  contains 2a1’, both s and 𝑑𝑧 2 orbitals are necessary for hybridization. Similarly, the pz orbital is also
essential for hybridization. Any one set of (px, py) or (𝑑𝑥 2 −𝑦 2 , 𝑑𝑥𝑦 ) is enough. Hence the possible hybridizations
are dsp3 and d3sp. Both the hybridizations on the central phosphorous atom can give rise to trigonal
bipyramidal molecule. (i) dsp3 (s, px, py, pz, 𝑑𝑧 2 ) and (ii) d3sp (s, pz, 𝑑𝑧 2 , dxy, 𝑑𝑥 2 −𝑦 2 ).
Since p-orbitals are lower in energy than d-orbitals, the dsp3 hybridization appears to be more realistic.
Construction of SALCs
Let us consider constructing pendent atom 𝜎-SALCs for trigonal bipyramidal AB 5 molecule, PCl5. The
expressions for these SALCs can be used to formulate equations for the dsp 3 hybrids on the central atom
phosphorous. The reducible representation for the 𝜎-SALCs is Γ𝜎 = 2𝐴1′ + 𝐸′ + 𝐴′′ 2.
For the trigonal bipyramidal structure we know that no operation of D 3h can convert one of the
equatorial positions (1, 2, and 3) into either of the axial positions (4 and 5) and vice versa. Consequently,
applying a projector operator to an equatorial reference basis function can only yield a SALC in terms of 𝜎1 , 𝜎2
and 𝜎3 . Likewise applying a projection operator to an axial reference function can only yield a SALC in terms of
𝜎4 and 𝜎5 . Thus, if we choose to use projection operators, we are forced to break up the hybrids into two sets.
We recognize that Γ𝜎 can be seen as the sum of Γ𝑒𝑞 and Γ𝑎𝑥 , where Γ𝑒𝑞 = 𝐴1′ + 𝐸′ and Γ𝑎𝑥 = 𝐴1′ + 𝐴′′ 2 . Thus, we
can generate separate sets of SALCs for the two kinds of positions.
The SALCs for equatorial sets can be generated using projection operator as follows. The SALC for
totally symmetric representation 𝑎1′ will be obtained as,
1 1 1
𝜓1(𝑎1′ ) = 𝜎1 + 𝜎2 + 𝜎3 ……. (1)
√3 √3 √3
Now the two degenerate SALCs of 𝑒 ′ symmetry will be,
2 1 1
𝜓2(𝑒 ′𝑎 ) = 𝜎1 − 𝜎2 − 𝜎3 …….. (2)
√6 √6 √6
1 1
𝜓3(𝑒 ′𝑏 ) = 𝜎2 − 𝜎3 ……… (3)
√2 √2
The two SALCs for the axial position only involve positive and negative combination of 𝜎4 and 𝜎5 . Therefore,
1 1
𝜓4(𝑎1′ ) = 𝜎4 + 𝜎5 ……. (4)
√2 √2
1 1
𝜓5(𝑎2′′ ) = 𝜎4 − 𝜎5 ………. (5)
√2 √2
The AOs on the central atom with matching symmetry are,
𝑠 ⇒ 𝑎1′ , (𝑝𝑥 , 𝑝𝑦 ) ⇒ 𝑒 ′ , 𝑝𝑧 ⇒ 𝑎2′′ and 𝑑𝑧 2 ⇒ 𝑎1′ . Using the above 5 equations we can write down the
transformation matrix for these AOs as,
8
𝑠 1 1 1 𝜓1
0 0
√3 √3 √3
2 1 1
𝑝𝑥 − − 0 0 𝜓2
√6 √6 √6
1 1
𝑝𝑦 = 0 − 0 0 𝜓3 ……. (6)
√2 √2
1 1
𝑝𝑧 0 0 0 − 𝜓4
√2 √2
1 1
[𝑑𝑧 2 ] [0 0 0
√2 √2 ] [𝜓5 ]
Inverting the transformation matrix (6) by taking the transpose of the 5 × 5 matrix in (6) we get,
𝜓1 1 2 𝑠
0 0 0
√3 √6
1 1 1
𝜓2 − 0 0 𝑝𝑥
√3 √6 √2
1 1 1
𝜓3 = − − 0 0 𝑝𝑦 ……… (7)
√3 √6 √2
1 1
𝜓4 0 0 0 𝑝𝑧
√2 √2
1 1
[𝜓5 ] [0 0 0 − [𝑑𝑧 2 ]
√2 √2]
From (7) we get expressions for the hybrid orbitals as,

1 2
𝜓1 = 𝑠 + 𝑝𝑥
√3 √6
1 1 1
𝜓2 = 𝑠 − 𝑝𝑥 + 𝑝𝑦
√3 √ 6 √2
1 1 1
𝜓3 = 𝑠 − 𝑝𝑥 + − 𝑝𝑦
√3 √6 √2
1 1
𝜓4 = 𝑝𝑧 + 𝑑𝑧 2
√2 √2
1 1
𝜓5 = − 𝑝𝑧 + 𝑑𝑧 2
√2 √2
One limitation of the SALCs obtained above is that the axial hybrids exclude contribution from the s-orbital and
the equatorial hybrids exclude contribution from 𝑑𝑧 2 orbital. In fact, the ideal set of 𝜎-SALCs for a trigonal
bipyramidal molecule should have the form,
𝜓𝑖 = 𝑁(𝑐𝑖1 𝜎1 ± 𝑐𝑖2 𝜎2 ± 𝑐𝑖3 𝜎3 ± 𝑐𝑖4 𝜎4 ± 𝑐𝑖5 𝜎5 ) where, 𝑖 = 1, 2, 3, 4, 5
The coefficients are non-zero except as required by symmetry. From the above approach the SALC for idealized
equal-bond trigonal bipyramid case is,
1
𝜓1 = (𝜎 + 𝜎2 + 𝜎3 + 𝜎4 + 𝜎5 )
√5 1
1
𝜓2 = (2𝜎1 − 𝜎2 − 𝜎3 )
√6
1
𝜓3 = (𝜎2 − 𝜎3 )
√2
1
𝜓4 = (𝜎4 − 𝜎5 )
√4
3 2
𝜓5 = {𝜎4 + 𝜎5 − (𝜎1 + 𝜎2 + 𝜎3 )}
√30 3
Ref. “Molecular Symmetry and Group Theory”, R. L Carter, p. 157


GT and Hybridization (S2)

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GT and Hybridization (S2)

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APPLICATIONS OF GROUP THEORY

Lecture notes: Dr. Cyriac Mathew Lecture notes

Determination of the type of hybridization:

To identify the various atomic orbitals undergoing hybridization, first we have

Hybridization scheme in sigma bonding – tetrahedral hybridization.

h = the order of the group

1.3.4 + 8.0.1 + 3.(−1).0 + 6.1.0 + 6.(−1).2

PROJECTION OPERATORS AND CONSTRUCTION OF SALCs

operator Pˆi to any one of the basis-functions  according to the expression,

The quantitative expressions for the sp 3 hybridized orbitals

(1,1,1) may be interpreted as the combination of unit vectors such

S4 x S 43x S4 y S 43y S4 z S 43z 12  34 13  24  23 14

Writing these equations as a transformation matrix we get,

inverse of equation (1). Let it be equation (2)

𝜓1 𝑏11 𝑏12 𝑏13 𝑏14 𝑠

Therefore, the individual sp3 hybrid orbitals are,

AB3 Type Molecules (eg. BF3)

Symmetry species a1’ e’

orbitals in triangular planar hybridization.

irreducible representation and R̂ is each of the operations of the

𝜓1 𝑏11 𝑏12 𝑏13 𝑠

AB5 Type Molecules (eg. PCl5)

D3h E 2C3 3C2  h 2S3 3 V

symmetry species are:

From (7) we get expressions for the hybrid orbitals as,

equal-bond trigonal bipyramid case is,

Ref. “Molecular Symmetry and Group Theory”, R. L Carter, p. 157

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