G 18001608

M.Sc DEGREE (CSS) EXAMINATION, JUNE 2018

Second Semester
Branch: Chemistry
AN2 C07/AP2 C07/CH2 C07/PH2 C07/POH2 C07-CHEMICAL BONDING AND
COMPUTATIONAL CHEMISTRY
[Common to all branches of chemistry]
(2012 Admission Onwards)
Time: Three Hours Maximum Weightage: 30
The scheme of valuation is only a guideline and any logically correct answer other than that
given in the scheme may be given due credit.
SECTION-A
Answer any 10 questions. Each question carries a weight 1
4 valuation points will fetch A-grade, 3 B-grade, 2 C-grade and 1 D-grade. Exceptions are
there in some cases and if the answer is complete full credit may be given even if the required
number of valuation points could not be identified.
1. Draw the MO energy level diagram of N2 molecule.

2. What is bond order? How it is calculated?

Bond order refers to the number of chemical bonds between two atoms, and
relates to the stability of the bond. Bonds are classified as single, double or triple. For
example, diatomic nitrogen (N2) has a triple bond between the two atoms (N≡N) while
acetylene (C2H2) has a bond order of three between the two carbon atoms and single
bonds between the carbon atoms and the hydrogen atoms (H−C≡C−H).
 −
=
2

3. What is correlation diagram as used in quantum mechanics?

The energies of MOs are often discussed with reference to a correlation
diagram. It shows these energies against the internuclear distance R. For high values of
R, the molecular orbitals become atomic orbitals of single atoms; for R → 0 they
approach the atomic orbitals of an "united atom" that emanates from an imaginary
fusion of the nuclei of both atoms. Thus, molecular orbitals are treated as a hypothetical
intermediate between two extremes already described in the basic theory of atomic
orbitals. The correspondence between AOs of the one and the other extreme is founded
on the criteria of energy and symmetry.
4. Apply SALC to water molecule.
Reducible representation is

SALCs are

5. What are Slater determinants?

It was pointed out by Slater that there is a simple way to write wavefunctions
guaranteeing that they will be antisymmetric for interchange of electronic space and
spin coordinates: one writes the wavefunction as a determinant. For lithium, it would be

6. Derive the spectroscopic term symbols for O2.

Derivation - correct steps - weightage 2
Correct term symbol - weightage 2
3
Σ
7. Write the z-matrix of butane.
C
C 1 1.5
C 2 1.5 1 110.0
C 3 1.5 2 110.0 1 60.0
H 1 1.0 2 110.0 3 300.0
H 1 1.0 2 110.0 3 180.0
H 1 1.0 2 110.0 3 60.0
H 2 1.0 1 110.0 3 120.0
H 2 1.0 1 110.0 3 240.0
H 3 1.0 2 110.0 1 180.0
H 3 1.0 2 110.0 1 300.0
H 4 1.0 3 110.0 2 60.0
H 4 1.0 3 110.0 2 180.0
H 4 1.0 3 110.0 2 300.0
8. What is ladder operator? What is its use?
 Successive application of Ladder operators on a function generates a series of
eigen functions and eigen values. They are also called raising and lowering operators,
shift operators or step-up or step-down operators.
First semester portion. Give full credit for any reasonable attempt
9. State and explain 'Non crossing rule in quantum mechanics.
• Non crossing rule is a useful principle in drawing correlation diagram.
• The atomic orbitals of the united atom together with the orbitals of the separated
atoms give rise correlation diagram.
• Non crossing rule states that for MO correlation diagram of many electron diatomic
molecules, the energies of the MO with the same symmetry cannot cross.
• The lowest MO of a given symmetry type must correlate with the lowest united atom
A.O of that symmetry and similarly for higher orbitals.

10. Explain the notation MP2/6-31G (d,p)/HF/6-31G.

A single point MP2 calculation using 6-31G(d,p) basis on a structure that was
optimized with the HF method using 6-31G basis is designated as MP2/6-
31G(d,p)//HF/6-31G. MP2 energy is the HF energy plus a correction term (a
peturbational adjustment) that represents lowering f energy brought about by allowing
the electrons to avoid one another better than in the HF treatment. The 6-31G (d,p)
basis set is a split valence basis set with polarisation functions for heavy atoms (d -
function) and p- function for hydrogen. HF/6-31G indicates geometry optimization
using HF method with 6-31G basis set.
11. Explain Hellmann-Feymann theorem.
The Feynamn-Hellmann theorem demonstrates the relationship between
perturbations in an operator on a complex inner product space and the corresponding
perturbations in the operator’s eigenvalue. It shows that to compute the derivative of an
eigenvalue with respect to a parameter of the operator, we need only know an
eigenvector and the derivative of the operator. The distribution of the electrons has
been determined by solving the Schrödinger equation, all the forces in the system can
be calculated using classical electrostatics. The theorem states that,

!
= "

where ! is the Hamiltonian operator depending upon a continuous parameter, is

the eigen state and is the eigen value of the state.

12. What is CHARMM? Explain its use in molecular mechanics.

CHARMM (Chemistry at HARvard Molecular Mechanics) is a highly
versatile and widely used molecular simulation program. It has been developed over the
last three decades with a primary focus on molecules of biological interest, including
proteins, peptides, lipids, nucleic acids, carbohydrates and small molecule ligands, as
they occur in solution, crystals, and membrane environments. For the study of such
systems, the program provides a large suite of computational tools that include
numerous conformational and path sampling methods, free energy estimators,
molecular minimization, dynamics, and analysis techniques, and model-building
 capabilities. In addition, the CHARMM program is applicable to problems involving a
much broader class of many-particle systems. Calculations with CHARMM can be
performed using a number of different energy functions and models, from mixed
quantum mechanical-molecular mechanical force fields, to all-atom classical potential
energy functions with explicit solvent and various boundary conditions, to implicit
solvent and membrane models.
13. Explain Kohn-Sham orbitals.
Kohn and Sham introduced orbitals into density–functional theory (DFT) as a
set of physically meaningless auxiliary quantities useful only for calculating the total
energy and charge density. The two basic ideas behind the KS approach are: (1) To
express the molecular energy as a sum of terms, only one of which, a relatively small
term, involves the “unknown” functional. (2) To use an initial guess of the electron
density r in the KS equations to calculate an initial guess of the KS orbitals and energy
levels and this initial guess is then used to iteratively refine these orbitals. The final KS
orbitals thus obtained are used to calculate an electron density that in turn is used to
calculate the energy.

SECTION-B
Answer any five questions. Each question carries a weight of 2.
8 to 7 valuation points will fetch A-grade, 6 to 5 B-grade, 4 to 3 C-grade and 2 to 1 D-grade.
Exceptions are there in some cases and if the answer is complete full credit may be given
even if the required number of valuation points could not be identified.

14. What are the important assumptions used in the HFSCF method for the determination
of the wave function and energy of a quantum many body system in a stationary state.
The Hartree-Fock Self Consistent Field approximation (HF SCF) provides an
excellent starting point to deal with a many-electron system and even if further
improvements on this are available and often employed, the HF SCF scheme itself
serves a very large number of applications. The methodology is applicable not only to
atoms/ions, but is readily extended to study other many-body systems, including
molecules, clusters, solids etc. Because of the central field approximation the energies
from these calculations are always greater than the exact energy and tend to a limiting
value called the Hartree Fock limit as the basis set is improved.
Advantage- It breaks the many electron Schrodinger equation into many
simpler one electron eqns. Each one electron equation is solved to yield a single
electron wave function called an orbital and an energy called an orbital energy. The
orbital describes the behavior of an electron in the net field of all the other electrons.
The second approximation in the Hartree Fock calculation is due to the fact
that the wave function must be described by some mathematical function which is
known exactly for only a few one electron systems. The functions used most often are
Gaussian type orbitals (GTO) e-ar2. The wave function is formed from linear
combination of atomic orbitals or basic functions. Because of this approximation most
Hartree Fock calculations give a computed energy greater than the Hartree Fock limit.
15. What are the important problems faced in quantum mechanical calculations for many
particles compared to a single particle? How it is overcome?
The exact solution of Schrodinger equation can be found for only a limited
number of problems, such as square wells, harmonic oscillator, hydrogen atom etc. A
majority of problems in quantum mechanics can usually be solved using a wide variety
of approximate methods. Here we will consider approximation methods that deal with
stationary states corresponding to the time-independent Hamiltonians: time independent
perturbation theory (non-degenerate and degenerate) and variational methods.
Perturbation theory applies to the cases where the Hamiltonian is only slightly different
from the Hamiltonian that can be exactly solved. When this difference or perturbation
is small then the approximate wavefunction and energy spectrum are obtained by
adding appropriate corrections to the wavefunction and energy of the exactly solvable
Hamiltonian. But often the Hamiltonian cannot be reduced to an exactly solvable and
perturbation parts and in those cases variational method becomes useful. It gives us
fairly good estimates of the energies of the ground state and a first few excited states
for which one has only qualitative knowledge of the wavefunctions.
16. Compare the molecular orbital theory (MOT) and valence bond theory (VBT). Give the
merits and demerits of the two theories in explain the properties of molecules.
• VBT was put forward by Heitler & London and later extended by Pauling
• MOT was introduced by Hund and Mulliken later extended by slater
• VBT starts with individual atoms and consider the interactions between them
• MOT starts with nuclei of constituent atom
• VBT may be considered as the direct translation of Lewis theory into the language
of quantum theory
• Both use linear combinations and variations principle but differ in the method of
choosing a trial wave function
• Ground state MO wave function of H2 is
$
#Mo = (ISa(1) ISa(2) + ISa(1) ISb(2)+ ISb(1) ISa(2) + ISb(1) ISb(2))
%&%'$%

The first two terms represent the covalent character and the last two terms
represent the ionic character. Simple MO treatment gives a bond energy which is far
behind the experimental value.

• The VBT allows to maintain their individuality in molecules

• The ground state wave function of VBT is
$
#UB = [#A(1)#B(2) ± #A(2)#B(1) ]
√%±%'$%

Both terms represent the covalent character of the bond. Covalent bond energy is far
below the experimental value.
• MOT makes no attempt to predict the shape of molecules. According to VBT each
covalent bond has a directional property
• MOT overestimates the ionic character whereas VBT underestimate these term by
neglecting them together
• MOT does not explain the dissociation of Ha atom
 • It is necessary to add further term to the VB wave function to improve at
#B = #cov + Χ #ionic
• MO Method can be improved by the method of configuration interaction.

17. Give the basic principles of Moller-Plesset perturbation theory.

In perturbation theory, one transforms the Schrodinger equation defined for
the exact Hamiltonian ! into an eigenvalue equation for an effective Hamiltonian ! eff.
For this purpose the Hilbert space associated with ! is split into a model space P
spanned by one (or more) reference functions (e.g. the HF wavefunction) and an
orthogonal space Q. The corresponding projection operators *+ and ,+ project out of the
exact wave function Ψ model function Φ(0) and correlation function χ. Furthermore,
operators *+ and ,+ are used to derive the effective Hamiltonian in form of the Feshbach-
Lowdin Hamiltonian. Applying the latter to the model function one obtains the exact
energy of the Schrodinger equation, i.e. despite the fact that one works only in model
space and, accordingly, has to solve a much simpler problem, perturbation theory
promises an exact energy. However, the difficulties are in the details: The Feshbach-
Lowdin Hamiltonian contains an inverse of the form (E − ,+ ! ,+)-1, which has to be
expanded in a suitable form to calculate the exact correlation energy stepwise, i.e. order
by order hoping that the perturbation series converges rapidly. In BWPT, this is done
by keeping the exact energy E in the inverse where of course E is not known thus
requiring an iterative solution. BWPT is exact for a 2-electron problem, has however
beside the computational burden the problem of not being size-extensive.
There is a hierarchy of Moller – Plesset energy levels – MP0,MP1,MP2 etc.
which successively account more thoroughly for the electronic repulsion.
MP0 – use electronic energy obtained by simply summing the Hartree – Fock one
electron energy. Ignores inter electronic repulsion- refuse to allow more than two
electrons in the same spacial MO.
MP1 – MP0 correlated with the coulomb and exchange integral. ie. MP1 is just the
Hartree – Fock energy.
MP2 – Hartree Fock energy + a correction term that represents a lowering of energy
brought about by allowing the electrons to avoid one another better than in the Hartree
Fock treatment.
18. State and prove variation theorem and apply it to a particle in a one dimensional box
using a suitable trial function.
A simple function that has satisfy the boundary conditions of one dimensional
box is the parabolic function
- = .( − .)
and the Hamiltonian is
ℏ% %
− 2 %3
2 .
But
4- ∗ 6 ! 6-7
=
8- ∗ |-:
For the numerator ad denominator
ℏ% < %
4- ∗ 6 ! 6-7 = − ; ( . − .%) % ( . − .%) .
2 = .
 ℏ% <
ℏ% >
=− ; (. − .) . =
%
= 6
< @
8- ∗ |-: = ; . ( − .) % %
.=
= 30
Substituting the values in the variation theorem
5ℎ% ℎ%
≤ = 0.1266515
$
4G % % %
But for particle in a one dimensionl bex
ℎ% ℎ%
= = 0.125
$
8 % %
The energy error is 1.3%
19. Calculate the symmetry adopted linear combinations (SALC) to the stretching
vibrations of C2h molecule.
Question not clear - Give credits for reasonable attempts to find SALCS
20. Write an input file for geometry optimization of water at HF/6-31G(d,p) level of theory
followed by frequency calculation in GAMESS.
$contrl runtyp=optimize $end
$statpt hssend=.t. $end
$contrl coord=zmt icharg=0 mult=1 $end
$contrl scftyp=RHF $end
$basis gbasis=n31 ngauss=6 ndfunc=1 npfunc=1 $end
$data
Water
Cnv 2

O
H 1 1.0
H 1 1.0 2 105.0
$end
21. What are generalized gradient approximation and local density approximation? Explain
the basic principles.
The simplest approximation is to assume that the density can be treated locally
as an uniform electron gas; the exchange correlation energy at each point in the system
is the same as that of an uniform electron gas of the same density. This approximation
was originally introduced by Kohn and Sham and holds for a slowly varying density.
Using this approximation the exchange-correlation energy for a density P(r) is given by
MNO
KL = ; P( )QKL (P) .
where εxc(P) is the exchange-correlation energy per particle of an uniform electron gas
of density

As the LDA approximates the energy of the true density by the energy of a local
constant density, it fails in situations where the density undergoes rapid changes such as
in molecules. An improvement to this can be made by considering the gradient of the
electron density, the so-called Generalized Gradient Approximation (GGA).
Symbolically this can be written as

KL = KL RP( ), ∆P( )T
This can lead to a large improvement over LDA results with accuracy approaching that
of correlated wavefunction methods such as MP2 and in some cases surpassing these.
While there is only one LDA there are several different parameterizations of the GGA.
 Some of these are semi-empirical, in that experimental data (e.g. atomization energies)
is used in their derivation. Others are found entirely from first principles.

SECTION – C
Answer any five questions. Each question carries a weight of 5.

20 to 17 valuation points will fetch A-grade, 15 to 13 B-grade, 10 to 8 C-grade and 5 to 4 D-

grade. Exceptions are there in some cases and if the answer is complete full credit may be
given even if the required number of valuation points could not be identified.

22. Give the molecular orbital (MO) treatment for the following molecules
(i) Be2 (ii) NO (iii) LiH

• Explanation of basic concepts of MO theory using MO treatment of H2 molecule -

Correct derivation - 10 points
• Brief discussion about other homonuclear and hetronuclear systems - 1 point
Since 2s and 2p AOs are rather close in energy they cannot be treated as non-
interactive. As a result, σ2s and σ2s* are lowered in energy and that σ2pzand σ *2pz are
raised in energy. ie σ2pz gets pushed above π2px= π2py. Thus the order is
σ1s< σ1s*< σ2s< σ2s*< π2px= π2py< σ2pz< π*2px= π*2py< σ* 2pz
this order holds for all the first row homonuclear diatomic molecules and the extend
of interaction decreases from Li2 to F2.

• Correct MO diagrams and explanation - 9 points (3 × 3 = 9 points)

(1) Be2 Molecule
Electronic configuration of Be is 1s2 2s2
2 Be [1s2 2s2] Be2[K K σ2s2 σ*2s2]
It is assumed that inner shell of atoms plays no effective part in molecular binding.
This means that when giving the E.C for a heavier molecule than H2 we can replace
σ1s2 σ*1s2 by K K meaning that both K shells are fully occupied.

(2) NO molecule
E.C of N is 1s2 2s2 2p3 and O is 1s2 2s2 2p4
NO [σ1s2 σ*1s2 σ2s2 σ*2s2 σ22pz G%UV
%
= G%UW
%
G%UV
∗%
]
 (3) LiH molecule

23. Compare the following calculations in quantum mechanics

(i) Density Functional Theory (DFT) methods
DFT has become very popular in recent years.

• It is computationally less intense than other methods with similar accuracy.

• The principal of DFT is that the energy of a molecule can be determined from
electron density instead of wave function.
• This theory originated with a theorem by Hohenberg and Kohn and practical
application of thin theory was developed by Kohn and Ham formulated a method
similar to that in a HF method.
• In this formulation the electron density is expressed as a linear combination of
basis function similar to HF orbital .A determinant is formed from these functions
called Kohn-Ham orbitals. It is the electron density from this determinant that is
used to compute the energy. KS orbital describes the behavior of electrons in a
molecule fast as the HF orbital.
The Hohenberg and Kohn theorem
 Every observable of a stationary quantum mechanical system can be calculated
from the ground state density alone i.e. every observable can be written as a
function of the ground state of the electron density .That is given the ground state
electron density function γ0(x,y,z) we can in principal calculate any grounds state
property
Eg: Energy E0.; γ0(x, y, z) E0
The electron density function will be given energy higher than the true ground state
energy. In DFT the electric energy from a trial electron density is the energy of the
electrons moving under the potential of the atomic nuclei.
The Kohn-Sham method (KS)
• Method of combining the wave function and electron density approach.
• The two basic ideas are:-
1. To express the molecular energy as a sum of terms, only one of which forms the
unknown functional .Thus even moderately large errors in this term will not induce
large error in the total energy.
2.To use an initial guess of the electron density γ in the K-S equation s, to calculate
an initial guess of the K-S orbitals and energy levels. The final K-S orbitals are
used to calculate an electron density that in turn is used calculate energy.
Types of calculations in DFT
• The local density approximation(LDA) - It is based on the assumption that at every
point in the molecule the electron density has the value that would be given by a
homogenous electron gas which has the same electron density.
• The generalized gradient approximation (GGA) - Most DFT calculations nowadays
use exchange correlation energy functional that utilize both the electron density
X X X
and its gradient.(XK + XZ + X[)γ= -∆γ
• Hybrid functional - Includes an energy contribution from the HF type electron
exchange .1st popular successful hybrid method was B3LYP.
(ii) Ab initio methods
These calculations are based on the Schrodinger equation. The Ab Initio
method solves the Schrodinger equation for a molecule and gives an energy and wave
function. The wave function is a mathematical function that can be used to calculate the
electron distribution. From the electron distribution we can tell things like how polar
the molecule is and which parts of it are likely to be attacked by nucleophiles or by
electrophiles. Ab Initio calculations are relatively slow
(iii) Molecular mechanics methods
Molecular mechanics is based on a model of a molecule as a collection of balls
(atoms) held together by springs (bonds). If we know the normal spring lengths and
angles between them, and how much energy it takes to stretch and bend the springs, we
can calculate the energy of a given collection of balls and springs i.i; of a given
molecule changing the geometry until the lowest energy is found enables us to do
geometry optimization ie, to calculate a geometry for the molecule. Molecular
mechanics is fast a fairly large molecule like a steroid (eg: cholesterol,C27H46O)can be
optimized in seconds on a good personal computer.
Molecular mechanics (MM) computes the structure and energy of molecules
based on nuclear motions. In this method electrons are considered explicitly, but rather
it is assumed that they will find their optimum distribution once the positions of the
nuclei are known. This assumption is a based on the Boen-Oppenheimer approximation
that nuclei are much heavier than electrons and their movement is negligibly small
 compared to the movement of e3lctrons. The molecular mechanics method (MM) also
called empirical force field (EFF) method is different from the semi empirical methods
The potential functions and the parameters used for evaluating interactions are
termed a force field and molecular mechanics methods are sometimes called force
fields methods. The term arises because the negative of the 1st derivative of the
potential energy of a particle with respect to displacement along some direction is the
force on the particle; a “force field” E(x, y, z coordination of atoms) can be
differentiated to give the force on each atom.

24. Give the general format of GAMESS and explain Basis set selection, method selection,
charge, multiplicity, single point energy calculation and frequency calculation.
GAMESS (General Atomic and Molecular Electronic Structure System) is an
ab initio and semiempirical computational chemistry program .The ab initio methods
available are RHF, UHF, ROHF, GVB, MCSCF along with MP2 and CI corrections to
those wave functions. MNDO, AM1 and PM3 are semiempirical Hamiltonians
available.
GAMESS can compute total energy, vibrational frequencies, transition structures ,
reaction coordinates, optical properties and a number of options for calculating
various other properties of atoms , molecules , ions etc. the input section of the
programme specifies the molecule, the calculational method to be used, the basis set,
the kind of calculation such as single point, geometry optimization, frequency and so
on. The GAMESS input files are modular and arranged in $. Most common input
groups are:
$ CONTRL – Specify basics of calculation such as execution type – run or check,
runtype – single point, optimization etc., coordinates- Cartesian or z-matrix ,charge,
multipliticity, scf type- RHF, UHF, ROHF etc.
$BASIS: specify basis set such as STO-Ng, 6-31G(d) etc.
$DATA: specify nuclear coordinate.
The point group of the molecule may be given or merely it may be given as C1. All
groups should end with $END. Anything could be given as title.
Frequency Calculation
$contrl runtyp=hessian $end
$contrl coord=zmt $end
$contrl icharg=0 mult=1 $end
$contrl scftyp=RHF $end
$basis gbasis=n31 ngauss=6 $end
$data
Water 1
Cnv 2

O
H 1 1.0
H 1 1.0 2 105.0
$end

Constrained Optimisation

$contrl runtyp=optimize nzvar=0 $end

 $zmat dlc=.t. auto=.t. ifzmat(1)= 1, fvalue(1)=0 $end
$contrl coord=zmt $end
$contrl icharg=0 mult=1 $end
$contrl scftyp=RHF $end
$basis gbasis=n31 ngauss=6 $end
$data
Water 2
Cnv 2

O
H 1 1.0
H 1 1.0 2 105.0
$end
Single point energy

$contrl runtyp=energy $end

$contrl coord=zmt $end
$contrl icharg=0 mult=1 $end
$contrl scftyp=RHF $end
$basis gbasis=n31 ngauss=6 $end
$data
Water 3
Cnv 2

O
H 1 1.0
H 1 1.0 2 105.0
$end

Geometry Optimisation

$contrl runtyp=optimize $end

$contrl coord=zmt $end
$contrl icharg=0 mult=1 $end
$contrl scftyp=RHF $end
$basis gbasis=n31 ngauss=6 $end
$data
Water 4
Cnv 2

O
H 1 1.0
H 1 1.0 2 105.0
$end

25. Using group theory explain the bonding in the following molecules:
(i) BF3 (ii) CH4
(i) BF3
The symmetric operations are E,2C3 ,3C2,σh,2S3,3σv
Reducible representation
Reduction of Reducible representation
nA1’= (1/12)[3-3-3+3]=0
nA2’= (1/12)[3+3-3-3]=0
nE’= (1/12)[6-6]=0
nA1”= (1/12)[3-3+3-3]=0
nA2”= (1/12)[3+3+3+3]=1
nA1’= (1/12)[6+6]=0
ҐRR = A2” + E”
The normalized SALC is

Φ3E’’ (p2) = (1/√6) [2p2-p3-p1]

But this SALC is not orthogonal to φ2 so cannot be taken. By applying POT on p3we
get
Φ4 =(1/√6)[2p3-p1-p2]
This is also not orthogonal to Φ2. So we try a linear combination of Φ3 & Φ4
Ie.Φ3 - Φ4 =√3/√2[ p2-p3]
On normalizing this wave function, we get
Φ3 =(1/√6)[p2-p3]
This is orthogonal to Φ2 as required. Sum of products of coefficients is zero. Thus the
complete set of SALCs for cyclopropenyl group are
φ1 =(1/√3)[P1+P2+P3]
φ2 = (1/√6)[2P1- P2-P3]
φ3=(1/√2)[P2-P3]

(ii) CH4

We can explain the hybridisation scheme for σ orbitals using tetrahedral CH4.
There are four CH bonds in the molecule directed towards the vertices of a
tetrahedron. First we have to find out the reducible representation for which the entire
set of σ orbitals as basis. The point group of tetrahedral CH4 molecule is Td.
The different symmetry operations of the Td point group are: E, 8C3, 3C2,
6S4 and 6σd. The reducible representation can be worked out from the rule that each
unshifted σ orbital during a symmetry operation contribute +1 to the character.

The RR for the Td point group using the 4 σ bonding orbitals as basis can be
represented as

This reducible representation can be reduced into the components using the standard
reduction formula and character table of Td point group.

Therefore
The quantitative forms of σ hybrid orbitals can be worked out using out inverse
transformation procedure. Let the hybrid orbitals be represented as Φ1, Φ2, Φ3 and
Φ4. The LCAO expressions for them are