Unit - I: Molecular structure and Theories of Bonding

Short Question and Answers

1. Write condition required for LCAO?
The conditions that are required for a linear combination of atomic orbitals are as follows:
 Same Energy of combining orbitals – The combining atomic orbitals must have same or nearly
same energy. This means that 2p orbital of an atom can combine with another 2p orbital of
another atom but 1s and 2p cannot combine together as they have appreciable energy difference.
 Same symmetry about the molecular axis – The combining atoms should have same symmetry
around the molecular axis for proper combination, otherwise, the electron density will be sparse.
For e.g. all the sub-orbitals of 2p have same energy but still, the 2p z orbital of an atom can only
combine with a 2pz orbital of another atom but cannot combine with 2p x and 2py orbital as they
have a different axis of symmetry.In general, the z-axis is considered as the molecular axis of
symmetry.
 Proper Overlap between the atomic orbitals – The two atomic orbitals will combine to form
molecular orbital if the overlap is proper. Greater the extent of overlap of orbitals, greater will be
the nuclear density between the nuclei of the two atoms.

2. Why are Antibonding orbitals higher in energy?

The energy levels of bonding molecular orbitals are always lower than those of anti-bonding
molecular orbitals. This is because the electrons in the orbital are attracted by the nuclei in the case
of bonding Molecular Orbitals whereas the nuclei repel each other in the case of the anti-bonding
Molecular Orbitals.

3. What are high spin and low spin complexes?

A complex is high spin or low spin depends on two main factors: the crystal field splitting energy
and the pairing energy. The electrons will take the path of least resistance: the path that requires the
least amount of energy. If the paring energy is greater than Δ, then electrons will move to a higher
energy orbital because it takes less energy. If the pairing energy is less than Δ, then the electrons
will pair up rather than moving singly to a higher energy orbital.
High spin complexes are ones with unpaired electrons and hence paramagnetic. These
compoundshave higher total spin number and hence are called high spin complexes. Low spin
complexes are diamagnetic ie without any unpaired electrons.
4. Write salient features of CFT.
Salient features of CFT:
 Metal ion and ligands are considered point charges.
 These interact by ionic (electrostatic) bonding.
 Ligands can be either negative point charges or neutral dipoles.
 Central metal ion is surrounded by ligands with 1/more lone pairs of electrons.
 There is no orbital overlap between metal ion and ligand.
5. Write the factors affects d-orbitals splitting. 
The d-orbitals splitting is affected by the following factors:
 The nature of the ligands. The stronger the ligand, the greater is the splitting.
 Oxidation state of the central metal ion. A higher oxidation state leads to larger splitting. 
 Size of d orbitals (i.e., transition series).
 Geometry of the complex.

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6. Arrange the species O2, O2-, O22-,O2+ the decreasing order of bond order and stability.
Sol.  The bond order decreases in the order is O2+ >O2>O2->O22- so, we conclude stability is directly
proportional to bond order.
7. Mention some properties of semiconductors.
Properties of semiconductors are as follows
i. It has covalent bonding.
ii. It is crystalline.
iii. It has a negative temperature coefficient of resistance.
iv. Its conductivity increases with the addition of impurities.
8. Distinguish between a metal an insulator and semiconductor.
Conductor (metals), semiconductors and insulators are distinguished from one another on the basis
of Forbidden gap.
In metals, the Forbidden gap does not exist, as a conduction and valence bands touches each other. 
In insulators, The Forbidden band is about 6 eV while in Semiconductors it is about 1eV.
9. How does conductivity of semiconductor changes with rise of temperature.
At absolute zero all semiconductors are insulators. The valence band at absolute zero is completely
filled and there is no free electrons in conduction band. At room temperature, electron jump to the
conduction band due to thermal energy.  When the temperature increases, large number of electron
crosses over the Forbidden gap and jump from valence band to conduction band.
Hence, conductivity of semiconductor increases with temperature.
10. Difference between Intrinsic and Extrinsic Semiconductors

Intrinsic Semiconductor Extrinsic Semiconductor

Pure semiconductor
Density of electrons is equal to the density of holes
Electrical conductivity is low
Dependence on temperature only
No impurities
Impure semiconductor
Density of electrons is not equal to the density of holes
Electrical conductivity is high
Dependence on temperature as well as on the amount
of impurity
Trivalent impurity, pentavalent impurity

ESSAY QUESTION AND ANSWER

1. What are the postulates of Molecular Orbital Theory?

Postulates: According to MO theory;

1. The atomic orbitals combine (overlap) to form a new orbital known as molecular orbital. As a
result, the atomic orbitals lose their identity.
2. The molecular orbitals are the energy states of a molecule, in which the electrons of the molecule
are filled just like in case of atomic orbitals. (are the energy states of an atom in which the electrons
of the atoms are filled.)

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 3. An M.O gives electron probability distribution around a group of nuclei as (as M.O always contain
two nuclei)same as the atomic orbitals are the electron probability distribution around the single
nucleus.
4. Only those A.Os are combined to form M.Os which have comparable energy, and proper
orientations. For eg: 1s can combine with 1s and not with 2s as they have energy gap. Similarly, s-
orbital can combine with pz but not with px or py as the z-axis is inter nuclear axis and so oriented in
line of s-orbital but others are perpendicular.
5. The no. of M.Os formed are equal to the no. of A.Os combined.
6. When two A.Os combine, they form two new M.Os known as bonding molecular
orbital(B.M.O) and antibonding molecular orbital (A.M.O).
7. The, B.M.O has lower energy and hence greater stability than the corresponding A.M.O.
8. The B.M.Os are represented by σ,π,δ etc. while A.M.Os are represented by σ*, π*,δ* etc.
9. The shapes of molecular orbitals depends upon the type of the combining atomic orbitals.
10. The filling of M.Os takes place by same rule as for atomic orbitals. like they follow:
a) Aufbau’s Principle: MOs are filled in order of increasing energies.
b)Pauli’s exclusion Principle: MO can have maximum of two electrons and these must have
opposite spin
c) Hund's rule of maximum multiplicity:Pairing of electrons doesn’t take place until all the atomic
or molecular orbitals are singly occupied.

Q2 Write briefly about LCAO

Linear Combination of Atomic Orbitals (LCAO)
1. As per this method, the formation of orbitals is because of Linear Combination (addition or subtraction) of
atomic orbitals which combine to form the molecule. Consider two atoms A and B which have atomic
orbitals described by the wave functions ΨA and ΨB.
2. If the electron cloud of these two atoms overlaps, then we can obtain the wave function for the molecule
by a linear combination of the atomic orbitals ΨA and ΨB. The below equation forms two molecular orbitals.
ΨMO = ΨA + ΨB
Bonding Molecular Orbitals
--When the addition of wave function (in phase) takes
place, the type of molecular orbitals formed are
Bonding Molecular Orbitals. We can represent them
by ΨMO = ΨA + ΨB. They have lower energy than
atomic orbitals involved.

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Anti-Bonding Molecular Orbitals
Molecular orbital forms by the subtraction of wave
function (out of phase), the type of molecular orbitals
formed are antibonding Molecular Orbitals. We can
represent them as ΨMO = ΨA – ΨB. They have higher
energy than atomic orbitals. Therefore, the combination of
two atomic orbitals results in the formation of two molecular orbitals. They are the bonding molecular orbital
(BMO) and the anti-bonding molecular orbital (ABMO).
Relative Energies of Molecular Orbitals
 Bonding Molecular Orbitals (BMO) – Energy of Bonding Molecular Orbitals is less than that of
Anti Bonding Molecular Orbitals. This is because of the increase in the attraction of both the nuclei
for both the electron (of the combining atom).
 Anti-Bonding Molecular Orbitals (ABMO) – Energy of Anti Bonding Molecular Orbitals is higher
than Bonding Molecular Orbitals. This is because the electron tries to move away from the nuclei and
are in a repulsive state.
The conditions that are required for a linear combination of atomic orbitals are as follows:
 Same Energy of combining orbitals.
 Same symmetry about the molecular
 Proper Overlap between the atomic

3. Write Salient features of crystal field theory.

      Salient features of CFT:

1. In a complex central metal atom or ion is surrounded by various ligands.

2. Metal ion & ligands are considered point charges. Their interaction is purely electrostatics
(ionic).
3. Ligands are negatively charged ions or neutral molecules, having lone pair of electrons (i.e.
H2O, NH3).
4. When ligands approach to central metal, degeneracy of d-orbitals in metal removed due to repulsion
between metal & ligands & split into different energy levels (t2g or eg). 
The repulsion is more if ligands approach along the axis of d-orbitals & acquire higher
energy (eg in Δo or t2g in Δt).
While repulsion is less if ligands approach in between the axis of d-orbitals & acquire less
energy (t2g in Δo or eg in Δt). Thus difference between these splited energy is called crystal field
stabilizing energy (CFSE) & denoted by 10 Dq or small delta. 10Dq Value depends on geometry
of complexes.
5. Electrons of metal are filled in splited d-orbital. According to Hund's rule i.e. from lower energy
levels.
6. Since there is no orbital overlapping hence no covalent character in bonding.
7. The magnitude of CFSE depends on nature & number of ligands & also geometry of complex.
8. If CFSE > 0 then stable complex, if CFSE < 0 then unstable complex. 

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4. Write the difference between Bonding and Anti bonding Molecular Orbital’s.

Molecular Orbital Theory

Bonding Molecular Orbitals Anti-Bonding Molecular Orbitals

Molecular orbitals formed by the additive Molecular orbitals formed by the subtractive effect
effect of the atomic orbitals is called bonding of atomic is called anti-bonding molecular orbitals
molecular orbitals

Probability of finding the electrons is more in Probability of finding electrons is less in antibonding
the case of bonding molecular orbitals molecular orbitals. There is also a node between the
anti-bonding molecular orbital between two nuclei
where the electron density is zero.

These are formed by the combination of + and These are formed by the overlap of + with – part.
+ and – with – part of the electron waves

The electron density, in the bonding
molecular orbital in the internuclear region, is
high. As a result, the nuclei are shielded from
each other and hence the repulsion is very
less.
The electron density in the antibonding molecular
orbital in the internuclear region is very low and so
the nuclei are directly exposed to each other.
Therefore the nuclei are less shielded from each
other.

The bonding molecular orbitals are The corresponding anti-bonding molecular orbitals
represented by σ, π, δ. are represented by σ∗, π∗, δ∗.

5. Draw the molecular orbital diagram of N2, O2 and F2 molecules. Calculate its bond order and
predict its magnetic behaviour.
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6. Draw and explain π molecular orbital’s of butadiene.
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  The molecular orbital diagram for the π-molecular orbitals of butadiene as a result of combining
the π-molecular orbitals of two ethene molecules. This shows the effect of conjugation.
 1,3-Butadiene contains two double bonds that are conjugated.
 It is "built" from 4 sp2 hybridised C atoms, each contributing a p atomic orbital containing 1
electron combine to produce four π MOs ψ1, ψ2, ψ3* and ψ4*of increasing energy.
 Two of MOs are the bonding MOs (ψ1 and ψ2) which are lower in energy than the p atomic orbitals
from which they are formed, while two of the antibonding MOs (ψ3* and ψ4*) are higher in energy.
 The relative energies of these orbitals can be accounted for by counting the number of bonding and
anti-bonding interactions in each:
1. Ψ1 has bonding interactions between C1-C2, C2-C3 and C3-C4
Overall = 3 bonding interactions with three constructive interactionsand has zero node.
2. Ψ2has bonding interactions between C1-C2 and C3-C4 but anti-bonding between C2-C3
Overall = 1 bonding interaction with two constructive interactionsand has one nodes.
3. Ψ3 has bonding interactions between C2-C3 but anti-bonding between C1-C2 and C3-C4
Overall = 1 anti-bonding interaction with one constructive interactionsand has two nodes.
4. Ψ4 has anti-bonding interactions between C1-C2, C2-C3 and C3-C4
Overall = 3 anti-bonding interactions with zero constructive interactions and has three nodes.
 4 electrons are arranged, 1 from each of the original atomic p orbitals. They are all paired in the two
stabilised pi bonding orbitals, ψ1 and ψ2.  The highest occupied molecular orbital or HOMO is ψ2 in
1,3-butadiene (or any simple conjugated diene).

 In contrast, the anti-bonding ψ3* and ψ4*orbitals contain no electrons. The lowest unoccupied orbital
or LUMO  is ψ3 in 1,3-butadiene (or any simple conjugated diene).

7. Draw and explain π molecular orbital’s of benzene.

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Benzene consists of 6 carbon atoms, all sp 2 hybridized, leaving one 2p orbital for π-bonds. The linear combination
of benzene's six 2p atomic orbitals, which are perpendicular to the ring plane, yields 6 molecular π orbitals. Three
bonding (ψ1, ψ2, ψ3) and three antibonding (ψ4*, ψ5*, ψ6*) π molecular orbitals.
Ψ1: The lowest energy MOs for benzene have zero nodes between the individual orbitals.In this orbital,
electrons are delocalized over the length of the molecule, resulting lowering of energy.All the p-orbitals are
aligned with phases pointing in the same direction.
 Has 6 bonding interactions with six constructive interactions and has zero node.

Ψ2&Ψ3: These two molecular orbitals have the same number of nodal planesi.e. one and therefore have the same
energy. Hence the orbitals are degeneratewhich results in lowering of energy.
 Has 4 bonding interactions but have 2 anti-bonding interactions therefore overall 1 bonding interaction
with four constructive interactions and has one nodes.

Ψ4&Ψ5:These two molecular orbitals has two nodal planes. Two ways to do it: cut through the bonds, or cut
through the atoms. Again, these are of the same energy.
 Has 2 bonding interactions but have 4 anti-bonding interactions therefore overall2 anti-bonding
interaction with two constructive interactions and has two nodes.

Ψ6: The Highest Energy molecular orbitals have p orbitals with completely alternating phases which three nodal
plane. This orbital has zero overlap between adjacent p-orbitals and therefore electrons in this orbital have
the minimum possible delocalization. They are therefore the highest energy.
 Has 6 anti-bonding interactions with zero constructive interactions and has three nodes.

8. Explain Splitting of d- orbital’s in octahedral complexes.

1. In octahedral complexes six ligands occupy at each vertices of

octahedron as shown in following figure.

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 2. As the ligands approaches to central metal ion then degeneracy of d-orbital of central metal is
removed by repulsion between electrons of metal & electrons of ligands.
3. The energy of d-orbital is splited between eg (dx2-y2& dz2) & t2g (dxy, dyz, dxz).
4. The energy level of eg is higher than t2g because there is more repulsion in eg due
to approach of ligands along the axis. The energy gap (CFSE) between eg& t2g is 10Dq.     
5. From the figure the energy of eg is higher by 6Dq or 0.6 delta zero from barrier center& energy
of t2g is lower by 4Dq or 0.4 delta zero from barrier center. Thus total energy obtained by filling
of electrons in eg& t2g gives the value of crystal field stabilizing energy (CFSE).
6. The magnitude of 10 Dq depends on geometry & nature of ligands.
For strong field ligands, splitting would be large & hence value of 10 Dq would be high. 
For weak field ligands, splitting would be less & hence value of 10 Dq would be low.
The d-orbitals will thus split as shown below:

9. Explain splitting of d- orbital’s in Tetrahedral Complex.

1. The tetrahedral arrangement of four ligands surrounding the metal
ions is as shown in the figure.
2. A regular tetrahedron is a cube. One atom is at the centre of the cube
and four of the eight corners of the cube are occupied by ligands.
3. The directions x, y and z point to the face centres. The dx2-y2 and
dz2 orbitals point along the x, y and z directions and dxy, dzx and dyz
orbitals point in between x, y and z directions.
4. The direction of approach of ligands does not coincide exactly with either the eg or t2g orbitals.
5. The t2g orbitals are pointing close to the direction in which the eg orbitals are lying in between the
ligands.
6. As a result, the energy of t2g orbitals increases compared to the energy of eg orbitals. Thus, d orbitals
again split into two sets- triply degenerate t2g of higher energy and doubly degenerate e orbitals of
lower energy.
7. That is, t2g orbitals are raised by 0.4 Δt in energy and the eg orbitals are stabilized by 0.6 Δt in
energy. 
8. The energy difference between the two sets of orbitals (Δt) will be about half the magnitude of that in
an octahedral complex (Δo).
 The d-orbitals will thus split as shown below:
 

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10. Explain splitting of d- orbital’s in ield theory to Square planer complex

1. Square planar coordination can be imagined to result when two ligands

on the z-axis of an octahedral are removed from the complex, leaving
only the ligands in the x-y plane. As the z-ligands move away, the
ligands in the square plane move a little closer to the metal.
2. The orbital splitting diagram for square planar coordination can thus be
derived from the octahedral diagram. As ligands move away along the
z-axis, d-orbitals with a z-component will fall in energy.
3. The dz2 orbital falls the most, as its electrons are concentrated in lobes along the z-axis. The dxz and
dyz orbitals also drop in energy, but not as much. Conversely, the dx2-y2 and the dxy orbitals increase
in energy.

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 4. The splitting diagram for square planar complexes is more complex than for octahedral and
tetrahedral complexes, and is shown below with the relative energies of each orbital.

  
11. Explain about different types of semiconductors.
Ans: Types of semiconductors
Semiconductors can be classified as:
1, Intrinsic Semiconductor 2, Extrinsic Semiconductor

Intrinsic Semiconductor
A semiconductor is an extremely pure form is
known as intrinsic semiconductor. In this case,
the holes in the valence band are vacancies
created by electrons that have been thermally
excited to the conduction band and electron hole
pairs are created. When electric field is applied
across an intrinsic semiconductor, the current
conduction takes place by two processes
namely; by free electron and holes. The free
electrons are produced due to the breaking up of
some covalent bonds by thermal energy. At the
same time, holes are created in the covalent
bond. Most common type of intrinsic
semiconductor elements are Germanium (Ge)
and Silicon (Si).

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Extrinsic semiconductor
The conductivity of semiconductors can be greatly improved by introducing a small number of
suitable replacement atoms called IMPURITIES. The process of adding impurity atoms (having 3 or
5 valence electrons) to the pure semiconductor (having 4 Valence Electrons) is called DOPING. The
purpose of adding impurity is to increase either the number of free electrons or holes in the
semiconductor crystal. Usually, only 1 atom in 107 is replaced by a dopant atom in the doped
semiconductor.
Depending upon the type of impurity added, extrinsic semiconductor are classified into two types that
is,
a. N-type semiconductor
b. P-type semiconductor

12. Explain about P- type and n-type semiconductors.

N-type semiconductor
When a small amount of pentavalent impurity (having 5 Valence Electrons) is added to a pure
semiconductor it is known as n-type semiconductor. By
this a large number of free electrons are produced in the
semiconductor crystal. 
The fifth electron of the dopant is set free. Thus the
impurity atom donates or provide a free electron for
conduction in the lattice and is called “Donar“.
Since the number of free electron increases by the addition
of an impurity, the negative charge carriers increase.
Hence it is called n-type semiconductor.
Typical examples of pentavalent impurities are arsenic, antimony, Bismuth, Phosphorus etc.
When a pure semiconductor (Silicon or Germanium) is doped by pentavalent impurity then, four
electrons out of five valence electrons bonds with the four electrons of Ge or Si.
The fifth electron of the dopant is set free. Thus the impurity atom donates a free electron for
conduction in the lattice and is called “Donar“.
Since the number of free electron increases by the addition of an impurity, the negative charge carriers
increase. Hence it is called n-type semiconductor.
b. P-type semiconductors
When a small quantity of trivalent impurity (having 3 Valence Electrons) added to a pure
semiconductor it is called P-type semiconductor.  This leaves an absence of electron (hole) in the
impurity. These impurity atoms which are ready to accept bonded electrons are called “Acceptors“.
Typical examples of trivalent impurities are Boron, aluminium, gallium, indium etc. 
With the increase in the number of impurities, holes (the positive charge carriers) are increased. Hence,
it is called p-type semiconductor.
Crystal as a whole is neutral, but the acceptors become an immobile negative ion. As conduction is due
to a large number of holes, the holes in the p-type semiconductor are MAJORITY CARRIERS and
electrons are MINORITY CARRIERS.
Applications of Semiconductors

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 Semiconductors are used in almost all electronic devices and as components transistors, diodes, photo
sensors, microcontrollers, integrated chips.

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