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STUDY MATERIAL
ENGINEERING CHEMISTRY (BBS00010)

Table of Contents

MODULE I: ATOMIC & MOLECULAR STRUCTURE

● Schrödinger equation.
● Particle in a 1D-box solution and their applications to a simple system.
● Crystal field theory and the energy level diagram for transition metal ions and their magnetic
properties.
● Molecular orbital diagram of homo nuclear diatomic molecules.
● Pi-molecular orbitals of butadiene and benzene and aromaticity.
● Band structure of solids and the role of doping on band structures.

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SCHRÖDINGER WAVE EQUATION

Schrödinger wave equation is a mathematical expression describing the energy and position of the
electron in space and time, considering the matter-wave nature of the electron inside an atom.

It is based on three considerations. They are:

● Classical plane wave equation,

● de-Broglie’s Hypothesis of matter-wave, and
● Conservation of Energy.

If an electron has wave-like properties, it must be described by a wave function, 𝚿.

2𝜋𝑥
𝛹 = 𝐴𝑠𝑖𝑛 ( ) … . . (𝑖)
𝜆
Where, λ is wavelength, x is displacement and A is constant.

Differentiating equation (i) we get

𝑑𝛹 2𝜋 2𝜋𝑥
= 𝐴𝑐𝑜𝑠 ( ) … . . (𝑖𝑖)
𝑑𝑥 𝜆 𝜆
Again, differentiating equation (ii) we get

𝑑2 𝛹 4𝜋2 2𝜋𝑥
2
= − 2
𝐴𝑠𝑖𝑛 ( ) … . . (𝑖𝑖𝑖)
𝑑𝑥 𝜆 𝜆
From equation (i) and equation (iii) we can get

𝑑2 𝛹 4𝜋2
= − 𝛹
𝑑𝑥 2 𝜆2
The above equation implies that electrons only move in one direction and behave as a wave.

𝑑2 𝛹 4𝜋 2
𝑂𝑟, + 𝛹=0 … . . (𝑖𝑣)
𝑑𝑥2 𝜆2
The above equation is applicable for all particles in a wave-like motion.

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ℎ
According to de-Broglie’s equation, 𝜆 = 𝑚𝑣

Where λ is wavelength, m is mass of electrons, v is velocity of light, and h is Planck constant.

Putting the value of λ in equation (iv) we get

𝑑2 𝛹 4𝜋 2 𝑚2 𝑣 2
𝑂𝑟, + 𝛹=0 … . . (𝑣)
𝑑𝑥2 ℎ2

Now the total energy of an electron, E is

E = Kinetic energy (K) + Potential energy (V)

So, K = E – V

1
Again, we know that kinetic energy, 𝐾 = 2 𝑚𝑣 2

1
So, E – V = 𝑚𝑣 2
2

2
Or, 𝑣 2 = 𝑚 (𝐸 − 𝑉) … . . (𝑣𝑖)

Thus, from equation (v) and equation (vi) we get

𝑑2 𝛹 8𝜋2 𝑚
+ (𝐸 − 𝑉) 𝛹 = 0
𝑑𝑥 2 ℎ2
The above equation, so derived, is the time independent Schrödinger wave equation in one
dimension, i.e., along the x-axis only.

For three-dimension, the time independent Schrödinger wave equation in compressed form can be
expressed as

𝑑 2 𝛹 𝑑2 𝛹 𝑑 2 𝛹 8𝜋 2 𝑚
+ + + (𝐸 − 𝑉) 𝛹 = 0
𝑑𝑥 2 𝑑𝑦 2 𝑑𝑧 2 ℎ2
ℎ2 𝑑2𝛹 𝑑2 𝛹 𝑑2𝛹
𝑂𝑟, − ( + + ) + 𝑉 𝛹 = 𝐸𝛹
8𝜋 2 𝑚 𝑑𝑥 2 𝑑𝑦 2 𝑑𝑧 2

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ℎ2
𝑂𝑟, [− 2 𝛻 2 + 𝑉] 𝛹 = 𝐸𝛹
8𝜋 𝑚
2 2 2 2
̂ = (− ℎ2 𝛻 2 + 𝑉) and 𝛻2 = ( 𝑑 2 + 𝑑 2 + 𝑑 2) is the Laplacian operator. Hence,
Where 𝐻 8𝜋 𝑚 𝑑𝑥 𝑑𝑦 𝑑𝑧

Important points:

● Solving the Schrodinger equation, we get the significant solution for the total energy (E) which is also
known as Energy Eigen value (E).
● Acceptable wave functions (Ψ) must have the following properties:
a. Ψ must be single-valued and finite, i.e., for each value of the variables x, y, z, there is only one
definite value of Ψ.
b. Ψ must be continuous.
c. Ψ must become zero at infinity.

Physical significance of Ψ and Ψ2

The wave function (Ψ) does not have any physical significance but it has only mathematical
significance. It always represents the amplitude, i.e., the displacement of electrons above or below the
mean value of some property. That’s why it is also known as amplitude function.

The absolute square of wave function (Ψ2) has physical significance as it gives the probability of
finding the electron at any region inside the atom. This probability is directly related to the density of
electron cloud, Ψ2 is also known as Probability Density. This further gives the idea of atomic orbitals.

A zero value of Ψ2 at a fixed point means the probability of finding electron at that point is zero and
is known as a Node.

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PARTICLE IN A ONE-DIMENSIONAL BOX

A particle in a one-dimensional box is a fundamental quantum mechanical approximation describing

the translational motion of a single particle confined inside an infinitely deep well from which it cannot
escape. The solutions to the problem give possible values of E and Ψ that the particle can possess. E
represents the allowed energy levels and Ψ(x) is a wave function, which when squared gives us the
probability of locating the particle at a certain position within the box at a given energy level.

We assume that the potential energy is zero inside the box (V = 0 for 0 < x < L) and the walls have
infinite potential energy to ensure that the particle has zero probability (Ψ2 = 0) of being at the walls or
outside the box, i.e., (V = ∞ for x ≤ 0 or x ≥ L).

One dimensional potential Box

One-dimensional Schrödinger wave equation for the above problem can be written as

ℎ2 𝑑 2 𝛹
− 2 + 𝑉 𝛹 = 𝐸𝛹
8𝜋 𝑚 𝑑𝑥 2
When the potential energy inside the box is zero, the above equation becomes

𝑑2𝛹 8𝜋 2 𝑚
= − 𝐸𝛹
𝑑𝑥 2 ℎ2
Solving the above equation, we get,

𝑛2 ℎ2
𝐸𝑛 = 𝑊ℎ𝑒𝑟𝑒 𝑛 = 1, 2, 3, …
8𝑚𝐿2

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This equation gives very important result and tells us that

1. The energy of a particle in 1-D box is quantized.

2. The lowest possible energy of a particle is NOT ZERO even at zero Kelvin temperature. This
is known as the zero-point energy (ZPE) and means the particle can never be at rest because it
always contains some energy. Hence at n = 1,
ℎ2
𝐸1 = … . . 𝑧𝑒𝑟𝑜 − 𝑝𝑜𝑖𝑛𝑡 𝑒𝑛𝑒𝑟𝑔𝑦 𝑣𝑎𝑙𝑢𝑒
8𝑚𝐿2

This is also consistent with Heisenberg's Uncertainty Principle; if the particle had zero energy, we
would know where it was in both space and time.

The probability of finding a particle at a certain point inside the box is determined by squaring Ψ.
The probability distribution for a particle in a box at the n = 1 and n = 2 energy levels looks like this:

Notice that the number of nodes increases with increasing energy level n. Also note that as the
energy of the particle becomes greater, the quantum mechanical model breaks down as the energy levels
get closer together and overlap, forming a continuum. This continuum means the particle is free and can
have any energy value. At such high energies, the classical mechanical model is applied as the particle
behaves more like a continuous wave. Therefore, the particle in a box problem is an example of wave-
particle duality.

Note: Number of node(s) for a given energy level ‘n’ = (n – 1)

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CRYSTAL FIELD THEORY

Assumptions of crystal field theory:

1. The metal and ligands are considered as point charges. Metal atom/ions are regarded as point positive
charges and the ligands as point negative charges or ionic dipoles.
2. There is no orbital-orbital interaction between metal and ligand. The bond between metal and ligand is
purely ionic due to electrostatic interaction.
3. The ligands remain separated in space around the metal atom/ion such that there is minimum repulsion
between them.

In order to understand clearly the crystal field interactions in transition metal complexes, it is
necessary to have knowledge of the geometrical or spatial orientation of d-orbitals. The d-orbitals are five-
fold degenerate in a free gaseous metal ion. If a spherically symmetric field of negative ligand field charge
is imposed on a central metal ion, the d-orbitals will remain degenerate but it gets splitted into two sets (i.e.,
t2g and eg or e and t2). A summary of the interactions is given below.

There are 5 d-orbitals, viz., dxy, dyz, dzx, dx2-y2 and dz2. Among these, three d-orbitals, dxy, dyz, and
dzx, lies in-between the axes and two d-orbitals, dx2-y2 and dz2, lies along the axes.

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Orientation of the d-orbitals in space

High Spin complex and Low Spin complex

The complex ion with the greater number of unpaired electrons is known as the high spin complex
whereas the low spin complex contains the lesser number of unpaired electrons. High spin complexes are
expected with weak field ligands in which the crystal field splitting energy (Δ) is smaller than the pairing
energy (P). The opposite applies to the low spin complexes in which strong field ligands cause maximum
pairing of electrons in the lower energy set due to large Δ.

● High spin complex – Maximum number of unpaired electrons. (P > Δ)

● Low spin – Minimum number of unpaired electrons. (Δ > P)

Example: [Co(CN)6]3- & [CoF6]3-

● [Co(CN)6]3- – Low spin complex.

● [CoF6]3- – High spin complex.

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Crystal Field Splitting in Octahedral Complex

● t2g – set of three orbitals (dxy, dyz and dxz) with lower energy.
● eg – set of two orbitals (dx2-y2 and dz2) with higher energy.

Crystal field splitting in octahedral complex

Crystal Field Splitting in Tetrahedral Complex

● e – set of two orbitals (dx2-y2 and dz2) with lower energy.

● t2 – set of three orbitals (dxy, dyz and dxz) with higher energy.

Crystal field splitting in tetrahedral complex

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Crystal Field Stabilization Energy (CFSE)

In an octahedral field, the energy difference between eg and t2g levels is given as Δ0 or 10Dq. It
states that each electron that goes into the lower t2g level stabilizes the system by an amount of –4Dq and
the electron that goes into eg level destabilizes the system by +6Dq. Similarly in the tetrahedral field, the e
level is lowered by –6Dq and the t2g level is raised by +4Dq. For example, the net change in energy for d5
and d10 systems in an octahedral field will be zero as shown below.

d5 : 3 (–4Dq) + 2 (+6Dq) = –12Dq + 12Dq = 0

d10 : 6 (–4Dq) + 4 (+6Dq) = –24Dq + 24Dq = 0

Table of CFSE

Octahedral complex Tetrahedral complex

Electronic Weak Strong Weak
configuration field/High CFSE (Dq) field/Low CFSE (Dq) field/High CFSE (Dq)
spin spin spin
d0 t2g0 eg0 0 t2g0 eg0 0 e0t20 0
d1 t2g1 eg0 –4 t2g1 eg0 –4 e1t20 –6
d2 t2g2 eg0 –8 t2g2 eg0 –8 e2t20 – 12
d3 t2g3 eg0 – 12 t2g3 eg0 – 12 e2t21 –8
d4 t2g3 eg1 –6 t2g4 eg0 – 16 + P e2t22 –4
d5 t2g3 eg2 0 t2g5 eg0 – 20 + 2P e2t23 –0
d6 t2g4 eg2 –4 t2g6 eg0 – 24 + 2P e3t23 –6
d7 t2g5 eg2 –8 t2g6 eg1 – 18 + P e4t23 – 12
d8 t2g6 eg2 – 12 t2g6 eg2 – 12 e4t24 –8
d9 t2g6 eg3 –6 t2g6 eg3 –6 e4t25 –4
d10 t2g6 eg4 0 t2g6 eg4 0 e4t26 0
[P = Pairing Energy]

Pairing energy: It is the amount of energy required to pair up the electrons in the corresponding orbital.
This is applied to complexes where the pairing energy is different with the type of ligands.

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Thus, the crystal field splitting depends on the field produced by the ligand and the charge on the
metal ion. An experimentally determined series based on the absorption of light by coordination compounds
with different ligands known as spectrochemical series has been proposed.

Spectrochemical series arranges ligands in order of their field strength as:

I– < Br– < Cl– < SCN– < F– < OH– < C2O42- < H2O < NCS– < EDTA4– < NH3 < en < NO2– < CN– < CO

Factors affecting the magnitude of Δ:

● Charge on the central metal ion: Higher the charge on the metal center, higher is the Δ. For example,
Δ(Cr3+) > Δ(Cr2+)
● Principal quantum number (n) of the central metal ion: Higher the n of the metal center, higher is
the Δ. For example, Δ(Ir3+) > Δ(Rh3+) > Δ(Co3+)
● Number of d-electrons: For the same charge on different metal centers, the lesser the number of d-
electrons, higher is the Δ. For example, Δ(Fe2+) > Δ(Co2+) > Δ(Ni2+)
● Strength of the ligand field: CFSE is generally higher for strong field ligands than that of weak field
ligands. For example, Δ for (CO) > Δ for (H2O)

Magnetic Properties of Coordination Complexes

We need to understand two concepts in terms of magnetic properties: paramagnetic and

diamagnetic.

Paramagnetic

Paramagnetic materials are weakly driven to a magnet or magnetic field. As a result, under the
influence of any magnetic field, paramagnetic materials are only faintly attracted. Aluminium and copper
are examples of this magnetic field.

Diamagnetic

Under the influence of a magnetic field, diamagnetic materials or substances will repel magnetism.
Glass and antimony are examples of diamagnetic.

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The extent of paramagnetism is measured in terms of the magnetic moment, μ. The larger the
magnitude of μ, greater the paramagnetism of the compound. Magnetic moment has contributions from
spin and orbital angular momentum. A non-spherical environment may lead to quenching of the
contribution from orbital angular momentum. However, the spin-only magnetic moment survives in all
cases and is related to the total number of unpaired electrons.

𝜇𝑒𝑓𝑓 = 𝜇𝑠𝑝𝑖𝑛−𝑜𝑛𝑙𝑦 = 2√𝑆(𝑆 + 1) = √𝑛(𝑛 + 2) 𝐵𝑀

Where n is the number of unpaired electrons and BM (Bohr Magneton) is the unit of magnetic
moment.

Magnetic Properties of Transition Metal Complexes

The magnetic behaviour of transition metal complexes with high spin metal ions is stronger than
that of those with low spin metal ions. This is due to the presence of more unpaired electrons in high spin
complexes, which results in a greater magnetic field. For example, the complex [Fe(H2O)6]2+ has a larger
magnetic field than the complex [Fe(CO)5]2+.

Electronic configuration of octahedral complexes

Formation of coloured ions

The energy of excitation corresponds to the frequency of the light absorbed. When an electron from
a low energy d-orbital is excited to a high energy d-orbital, light is absorbed. Hence, the characteristic
colour of the complex depends on the transmitted light, which is the complementary colour of the light
absorbed. Hence, the coordination complexes exhibit their colours due to the ‘d-d transition’.

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Μ.Ο. DIAGRAM OF HOMONUCLEAR DIATOMIC MOLECULES

As we know atoms combine through bond formation to form molecules, similarly atomic orbitals
combine with each other to form molecular orbitals. These molecular orbitals also contain electrons and
the electron filling in these MO’s follow aufbau principle, Hund’s rule and Pauli’s exclusion principle as
we have seen for atomic orbitals filling.

Features of MOs

● Include all the valence atomic orbitals on both atoms, whether they are empty or filled.
● Atomic orbitals must have the proper symmetry and energy to interact and form molecular orbitals.
● The total number of atomic orbitals must always equal the total number of molecular orbitals.
● Bonding molecular orbitals are more stable than the atomic orbitals and increase the electron density
between the nuclei.
● Antibonding molecular orbitals are less stable than the atomic orbitals and decrease the electron density
between the nuclei.

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● Fill the completed MO diagram with electrons according to the Aufbau principle, Hund’s rule and
Pauli’s exclusion principle.

First period diatomic molecules

Dihydrogen (H2)

To generate the molecular orbital diagram for H2, begin with the valence atomic orbitals. In the case
of H2, each H atom has a single 1s valence orbital. Then two s-orbitals overlap they form a σ bonding
combination and a σ* antibonding combination. The σ bonding molecular orbital increases the electron
density between the two H atoms and has no nodes, which makes this combination lower in energy than
the H 1s atomic orbitals. The σ* antibonding molecular orbital has a node between the two H atoms and
decreases the amount of electron density between the two H atoms, which makes this combination higher
energy than the H 1s atomic orbitals.

This is illustrated in the following figure. Notice that combining two 1s atomic orbitals has given
two MOs. Each H atom has one valence electron, so two electrons are placed in the σ bonding MO.

Electronic configuration of H2 is σ1s2

Bond order

Once filled with electrons, molecular orbital diagrams can be used to determine bond order in a
molecule. Bond order is defined as the difference between the number of electron pairs occupying bonding

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and antibonding orbitals in the molecule. A bond order of one is equivalent to a single bond, a bond order
of two is equivalent to a double bond, a bond order of three is equivalent to a triple bond, etc.

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑏𝑜𝑛𝑑𝑖𝑛𝑔 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 − 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑎𝑛𝑡𝑖𝑏𝑜𝑛𝑑𝑖𝑛𝑔 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠

𝐵𝑜𝑛𝑑 𝑜𝑟𝑑𝑒𝑟 = ( )
2
The above equation can be used to calculate the bond order of a molecule from its molecular orbital
diagram. In the H2 molecule there are two electrons in the sigma bonding MO and no electrons in the sigma
antibonding MO. Therefore, the bond order is (2-0)/2 = 1. This agrees with the picture of H2 from the Lewis
structure where the two H atoms are bonded by a single bond.

Other first period diatomic molecules:

Qualitatively, the molecular orbital diagrams H2, He2 and any ions of H2 will be the same because
they all will involve the overlap of two 1s atomic orbitals. What will change is the number of electrons in
the diagram, and therefore the bond order. Consider the two hydrogen ions, H2+ and H2- in the below figure.
The H2+ ion has one fewer electron than H2, meaning the sigma bonding MO has one single electron in it
and the sigma antibonding MO is still unoccupied. This results in H2+ having a bond order of 0.5. Non-
integer bond order doesn't have a direct equivalent in Lewis theory but a bond order of 0.5 tells you that the
molecule is (somewhat) stable relative to the two free atoms, but the bond will be weaker than a single
bond. From this we can predict that H2+ will have a longer bond and a lower bond dissociation energy than
H2. H2- has one more electron than H2, meaning the sigma bonding MO is filled and the additional electron
occupies the sigma antibonding MO. This arrangement of electrons also results in a bond order of 0.5, so
H2- is expected to have a bond strength and length similar to H2+.

In the case of He2, each He atom has two valence electrons so the completed MO diagram has two
electrons in the sigma bonding MO and 2 electrons in the sigma antibonding MO. With both the bonding
and antibonding MOs completely filled, He2 has a bond order of 0. This means that He2 isn't energetically
favorable relative to two He atoms, and should not exist. In practice, He2 can be observed at very low
temperatures, but the "bond" between the He atoms is better described as van der Waals forces than a
covalent bond.

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Electronic configurations: H2+ = σ1s1 H2– = σ1s2 σ*1s1 He2 = σ1s2 σ*1s2

Second Period Diatomic Molecules

The four simplest molecules we have examined so far involve molecular orbitals that derived from
two 1s atomic orbitals. If we wish to extend our model to larger atoms, we will have to contend with higher
atomic orbitals as well. One greatly simplifying principle here is that only the valence orbitals are needed
to be considered. Core atomic orbitals such as 1s are deep within the atom and well-shielded from the
electric field of a neighboring nucleus, so that these orbitals largely retain their atomic character when
bonds are formed. For second period molecules that means we need to consider the overlap of the 2s and
the 2p atomic orbitals.

Dioxygen (O2)

One major drawback of Lewis and valence bond theories are their inability to explain why O2 is
paramagnetic. To construct a molecular orbital diagram for O2 we have to consider the interactions between
both the 2s and 2p atomic orbitals on each oxygen atom. Because of oxygen’s high effective nuclear charge
and the penetration of the 2s orbital there is a large energy difference between the 2s and the 2p atomic
orbitals. This means the 2s and 2p atomic orbitals do not meet the energy criterion for overlap and cannot
mix together. We will consider the overlap of the 2s and 2p orbitals separately.

The energy of the 2s atomic orbitals in oxygen are lower and the radius is larger when compared to
the 1s orbitals of hydrogen, but qualitatively when two 2s orbitals overlap they will also form σ bonding
and σ antibonding molecular orbitals. The 2p orbitals can overlap to form both σ and π bonds. If we assume
the O-O bond is on the z-axis, this means the pz orbitals on each O atom will lie along the bond axis and

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overlap face to face (head on overlapping) to form σp bonding and σp* antibonding molecular orbitals. The
px and py atomic orbitals both lie parallel to the bond axis and overlap laterally to form a degenerate (same
energy) pair of πp bonding and πp* antibonding molecular orbitals. As there is less orbital overlap in π bonds
compared to σ bonds, the πp bonding MO is stabilized less than the σp bonding MO and the πp* antibonding
MO is less destabilized than the σp* antibonding MO as shown in the below figure. Each oxygen atom has
six valence electrons, and so the central MO diagram is filled with 12 electrons. This leaves two electrons
in the pair of πp* antibonding MOs, and to maximize spin multiplicity according to Hund's rule one is placed
in each of the MOs. Unlike the Lewis structure, the molecular orbital diagram for O2 shows that

Oxygen is paramagnetic, having two unpaired electrons, in agreement with experimental observations.
The MO diagram also predicts that O2 has a bond order of 2 [(8-4)/2 = 2] (O=O double bond) which agrees
with Lewis and valence bond theories as well as experimental bond length.

MO diagram of O2

Notice that Eσ > Eπ, because the σ bonds have more overlap than π bonds.

Just as with atoms, we can write a molecular electron configuration for O2 as

σ2s2 σ2s*2 σ2p2 π2p4 π2p*2

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LCAO-MO theory also predicts correctly that O2 has two unpaired electrons. Hence, oxygen is two
electrons paramagnetic.

Species Electronic configuration Bond order

O22+ σ2s2 σ2s*2 σ2p2 π2p4 π2p*0 (8 – 2)/2 = 3
O2 + σ2s2 σ2s*2 σ2p2 π2p4 π2p*1 (8 – 3)/2 = 2.5
O2 σ2s2 σ2s*2 σ2p2 π2p4 π2p*2 (8 – 4)/2 = 2
O2 - σ2s2 σ2s*2 σ2p2 π2p4 π2p*3 (8 – 5)/2 = 1.5
O22- σ2s2 σ2s*2 σ2p2 π2p4 π2p*4 (8 – 6)/2 = 1

Note: Bond order: O22- < O2- < O2 < O2+ < O22+

Bond strength or bond energy: O22- < O2- < O2 < O2+ < O22+

MO diagram of F2

Diatomic fluorine is made by the overlapping of the valence atomic orbitals of two different fluorine
atoms. Each valence shell of both fluorine contains seven electrons, thus the central MO of F2 contains a
total of 14 electrons arranged in accordance with Hund’s rule.

9F = 1s2 2s2 2p5

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Electronic configuration: σ2s2 σ2s*2 σ2p2 π2p4 π2p*4

Bond Order: (8 – 6)/2 = 1 (F–F single bond)

Electronic configuration of Ne2: σ2s2 σ2s*2 σ2p2 π2p4 π2p*4 σ2p*2

Bond Order: (8 – 8)/2 = 0, i.e., diatomic Neon molecule (Ne2) does not exist.

Hence, Neon is monatomic molecule.

Orbital Mixing

● Orbitals of similar but unequal energies can interact if they have the same symmetry.
● The 2s and 2pz orbitals form MOs have the same symmetry (σg and σu).
● sp mixing causes the σg and σu MOs to be pushed apart in energy.
● The σ and π orbitals change order in energy. (πb2py=2pz goes higher than σb2px)
● In homonuclear diatomic molecules, orbital mixing is very common in
elements with Z ≤ 7, whereas elements Z > 7 does not allow orbital mixing.

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Li2, Be2, C2, N2 O2, F2, Ne2

⮚ Electronic configuration of B2 : σ2s2 σ2s*2 π2p2 σ2p0 π2p*0 σ2p*0

BO = 1; thus, B2 is two electron paramagnetic.

⮚ Electronic configuration of C2 : σ2s2 σ2s*2 π2p4 σ2p0 π2p*0 σ2p*0

BO = 2; thus, C2 is diamagnetic (No unpaired electron is present).

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⮚ Electronic configuration of N2 : σ2s2 σ2s*2 π2p4 σ2p2 π2p*0 σ2p*0

BO = 3; thus, N2 is diamagnetic.

⮚ Electronic configuration of N2+ : σ2s2 σ2s*2 π2p4 σ2p1 π2p*0 σ2p*0

BO = 2.5; thus, N2+ is one electron paramagnetic.

⮚ Electronic configuration of N2- : σ2s2 σ2s*2 π2p4 σ2p2 π2p*1 σ2p*0

BO = 2.5; thus, N2- is one electron paramagnetic.

⮚ Similarly, B.O. of N22+ (0 electron paramagnetic) and N22- (2 electron paramagnetic) are 2 in each case.

Stability: N22- = N22+ < N2- = N2+ < N2

DRAWING THE PI-MOLECULAR ORBITALS OF CONJUGATED SYSTEM

● Pi-molecular orbitals are formed due to lateral overlapping of the p-orbitals.

● The number of molecular orbitals (n) for a pi-system is equal to the number of contributing p-orbitals.
Out of them half will be bonding orbitals and half will be antibonding.
● The lowest-energy orbital always has zero nodes between the p-orbitals (A “node” is where there
is a change in phase between adjacent p-orbitals (i.e, where they can’t constructively overlap). The
lowest energy level (the “ground floor”, if you will) has all the p-orbitals aligned the same way, and
therefore has zero nodes between the p orbitals (not counting the node inherent to the p-orbitals that
lies in the plane of the molecule). This provides the greatest possible delocalization of the electrons,
and hence is the lowest in energy.
● The number of nodes between p-orbitals increases by 1 for each successive energy level, such that
the highest-energy orbital has (n – 1) nodes (all phases of contributing p-orbitals alternate).
● The trick to drawing the orbital(s) of intermediate energy is to understand where to put the
node(s). Nodes are positioned in a way such that they are symmetrical relative to the centre. For
example, a system with 1 node has the node smack in the centre. A system with 2 nodes will have the
nodes at equal distance relative to the centre.

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The Butadienyl Pi System (n = 4)

Butadiene is composed of 4 carbons with two adjacent pi bonds. These two pi bonds are conjugated;
all four p orbitals are all aligned with each other, and build up into a larger pi system. It’s for this reason
that we can describe the electron density in butadiene with resonance forms, which show alternative
distributions of pi electrons in the molecule.

Since butadiene consists of 4 individual p orbitals, the pi-system of butadiene will contain 4 pi
molecular orbitals. Out of these two are bonding and two are antibonding orbitals. Now, let’s try to draw
out what each of these four molecular orbitals should look like.

1. The Lowest-Energy Molecular Orbital (π1) of the Butadiene Pi System has zero nodes.

2. The Highest-Energy Molecular Orbital (π4) has three nodes:

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3. The Second-Lowest-Energy Molecular Orbital (π2) has one node.

4. The Third-Lowest-Energy Molecular Orbital (π3) has two nodes.

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5. The full Molecular Orbital Diagram for the Butadienyl System (n = 4):

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6. Populating the Molecular Orbitals of Butadiene with electrons.

Butadiene has two double bonds with two electrons each, for a total of 4 pi electrons. We fill up the
lowest-energy molecular orbitals first, which gives us the following:

We have
highlighted
two
molecular
orbitals on
this diagram
as being of
particular
interest,
because, as
we will see,
they are
where the
reaction
usually
happens.
They are
called the
“frontier”
orbitals.

7. Identifying the “HOMO” and “LUMO” of Butadiene.

The highest occupied molecular orbital (HOMO) is π2. You can think of the HOMO as being a
little bit like the “valence electrons” of the pi system: they’re the most readily lost. If butadiene

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participates in a reaction where it is the electron-donor (nucleophile), its electrons are going to come
from that orbital.
The lowest unoccupied molecular orbital (LUMO) is π3. The LUMO is the lowest-energy
unoccupied orbital. If butadiene participates in a reaction where it is the electron acceptor (electrophile),
the electrons will be donated to that orbital.

The Benzene Pi System (n = 6)

1. The Lowest-Energy Molecular Orbitals of Benzene have zero nodes.

2. The highest energy level of the M.O. diagram has the maximum number of nodes.
In the case of cyclic systems, the (n – 1) rule fails. Drawing a molecular orbital of benzene with
5 nodes is impossible.

3. Where do we place the nodes in the intermediate energy levels of Benzene?

For the second energy level M.O there will be one node. But, it’s impossible to draw a cyclic pi
system with one node, but we can draw a system with one nodal plane. Here, for instance, we’ve drawn
a nodal plane that cuts through two of the single bonds:

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But wait! There’s actually a second way to do it. We can also draw a nodal plane through the atoms,
like this.

These two molecular orbitals (π2 and π3) have the same number of nodal planes, and therefore have
the same energy. The way we usually describe this in chemistry is by saying the orbitals are degenerate.
This is really the key difference in the molecular orbital picture of a cyclic system versus an acyclic
system: two units can co-exist on the same floor. For benzene, that results in a lowering of energy.

4. To draw the rest of the MOs

For benzene, the next level up (third energy level) has two nodal planes. Again, there’s two ways to
do it: cut through the bonds, or cut through the atoms. Again, these are of the same energy.

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5. The Benzene Molecular Orbital Diagram: Putting It All Together.

The final step is to arrange all the pi orbitals together and then to fill each level with electrons.
Here’s the complete molecular orbital picture for hexatriene:

● Degenerate π2 and π3 M.O’s are HOMO for benzene.

● Degenerate π4* and π5* M.O’s are LUMO for benzene.

⮚ Why is Benzene (cyclic) more stable than Hexatriene (acyclic)?

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A cyclic pi system allows for two ways to place a single nodal plane: through-bond, or through-
atom. In benzene, this means that the second and third MOs with the same energy – they are
“degenerate”. In chemistry terms, the highest occupied molecular orbitals (HOMO) of benzene are
lower in energy than the highest occupied molecular orbital (HOMO) of hexatriene. Hence, benzene is
more stable than hexatriene.

AROMATICITY

In terms of the electronic nature of the molecule, aromaticity gives a conjugated system often made
of alternating single and double bonds in a ring. This allows for the electrons in the molecule’s pi system
to delocalize around the ring by increasing the molecule’s stability.

Characteristics of Aromatic Systems

An aromatic ring has a set of covalently bound atoms with specific characteristics:

● A delocalized conjugated or pi system, an arrangement of alternating single and double bonds.

● Coplanar structure, with all the atoms in the same plane
● Contributing atoms should be arranged in one or more rings.
● A number of π delocalized electrons that is even, but not a multiple of 4. (4n + 2) π electrons,
where n = 0, 1, 2, 3, 4, 5, and so on. This is Huckel’s rule.
According to this rule, if a molecule has (4n + 2) π electrons then it is aromatic. If it has 4n π
electrons and has characteristics 1 to 3 as above, the molecule is antiaromatic. Benzene is

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aromatic with 6 electrons, from 3 double bonds, cyclobutadiene is antiaromatic because the
number of π delocalized electrons is 4 that is a multiple of 4.
● Aromatic molecules interact with each other in so-called π – π stacking. The π systems form two
parallel rings that overlap in a face-to-face orientation. Aromatic molecules are also interacting
with each other in an edge-to-face orientation.

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BAND THEORY OF SOLID

Band theory of solids describes the quantum state that an electron takes inside a metal solid. Every
atom comprises various discrete energy levels. In atoms, electrons are filled in respective energy orbits
following the Pauli’s exclusion principle. In metal a large number of atomic orbitals aggregate, thereby
forming an energy continuum called energy bands. Band theory helps to visualize the difference between a
conductor, semiconductor, and an insulator by plotting available energies for an electron in a material.

Energy Bands in Solids

In the band theory of solids, there are many energy bands but the following are the three most
important energy bands in solids:

● Valence Band,
● Conduction Band,
● Forbidden Band.

Valence Band

The energy band that consists of valence electrons energy levels, is known as the valence band. The
valence band is present below the conduction band and the electrons of this band are loosely bound to the
nucleus of the atom. For example, in Na metal, 3s energy band is the valence band.

Conduction Band

The energy band that consists of free electrons energy levels, is known as the conduction band. For
electrons to be free, external energy must be applied such that the valence electrons get pushed to the
conduction band and become free. For example, in Na metal, 3p energy band is the valence band.

Forbidden Band

The energy gap between the valence band and the conduction band is known as the forbidden band
which is also known as the forbidden gap. The electrical conductivity of a solid is determined by the
forbidden gap and also the classification of the materials as conductors, semiconductors, and insulators.

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Conductors, semiconductors and insulators

Depending on the gap between conduction band and valence band we can classify substances as
Conductors, semiconductors and insulators.

Conductors

A conductor is a type of material that allows the electric current to flow through it i.e. in case of
conductor, the valence and conduction bands overlap. All the metals are conductors. The resistance of
the conductors increases with the increase in the temperature. Hence, the conductor has a positive
temperature coefficient of resistance.

The conductors are used for making conducting wires and cables for carrying electric current.

Insulators

An insulator is a type of material that does not allow the electric current to pass through it, due to
its high electrical resistance. In the insulators, the energy gap between valence and conduction bands is very
large (about 15 eV). At room temperature, the valence electrons of the insulator do not have enough energy
to cross over to the forbidden energy gap. But, if the temperature is raised, some of the electrons may
acquire enough energy to cross over to the forbidden energy gap. Hence, the resistance of the insulator
decreases with the rise in temperature. Therefore, the insulator has negative temperature coefficient of
resistance.

Due to high electrical resistance, the insulators are used for protection against electric shocks.

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Semiconductors

The semiconductors are the materials having conductivity in-between conductors and insulators. In
a semiconductor, the forbidden energy gap between valence and conduction bands is very small (about 1
eV) as compared to insulators.

As temperature is increased, more valence electrons cross over to the energy gap to reach the
conduction band and the conductivity increases. This shows that electrical conductivity of semiconductors
increases with the rise in temperature. Hence, a semiconductor has a negative temperature coefficient of
resistance.

Difference between Conductor, Semiconductor and Insulator

Parameter Conductor Semiconductor Insulator

A material that allows A material that has Materials that do not
Definition electric current to pass conductivity in between allow the electric current
through it very easily. conductors and insulators. to pass through them.
No energy gap i.e. the
Forbidden Small energy gap (approx. Very large energy gap
conduction band overlaps
Energy Gap 1 eV). (approx. 15 eV).
the valence band.
Due to movement of both
Conduction Due to free electrons. electrons and holes No conduction.
(positive charge carriers).

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Temperature
Coefficient of Positive Negative Negative
Resistivity
Valence
Electrons in Less than 4 4 More than 4
Outermost Shell
Metals like silver (best
Silicon, Germanium, Air, Mica, Glass, Paper,
Examples conductor), gold, copper,
Gallium, Arsenide etc. Porcelain, Wood etc.
aluminium etc.

Doping in semiconductors

The conductivity of semiconductors can also be increased by adding some impurity in the pure
semiconductor material, called doping. The semiconductors are commonly used in manufacturing of solid
state electronic devices.

Pure Silicon or Germanium are rarely used as semiconductors. Practically usable semiconductors
must have a controlled quantity of impurities added to them. The process of adding an impurity to an
intrinsic or pure material is called doping and the impurity is called a dopant. After doping, an intrinsic
material becomes an extrinsic material. Practically only after doping these materials become usable.

Effect of doping by n-type material

The effect of doping by an n-type material is as follows –

● On addition of Arsenic (As) or Antimony (Sb) to pure Silicon, it becomes an n-type material.
● Arsenic atoms have additional electrons or negative charges that do not take part in the process of
covalent bonding. These extra electrons are referred to as donor impurities.
● Upon doping they are free to move about through the crystal structure and enhance the electrical
conductivity.
● Electrons are considered to be the majority current carriers in this type of crystal and holes are the
minority current carriers.

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Effect of doping by p-type material

The effect of doping on a p-type material is as follows –

● When Indium (In) or Gallium (Ga) is added to pure silicon, a p-type material is formed.
● This type of dopant material has three valence electrons. They form three covalent bonds while the
fourth place remains vacant as a hole.
● These holes are free to move about through the crystal structure. The movement of electrons are
considered as opposite to that of holes and enhance the electrical conductivity.
● Here holes are the majority current carriers and electrons are minority current carriers.

n-type semiconductor due to movement of excess of electrons

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p-type semiconductor due to movement of positive holes

MODEL QUESTIONS

1. Write the Schrödinger’s time independent wave equation.

2. What is the significance of Ψ2?
3. Molecular oxygen is paramagnetic in nature. Explain.
ℎ2
4. Show that [𝑉 − 8𝜋2𝑚 𝛻 2 ] 𝛹 = 𝐸𝛹
ℎ2
5. Prove that for a particle in a one-dimensional box at n = 1, the energy equation is 𝐸𝑛 = 8𝑚𝐿2 .

6. Predict the aromaticity of the following compounds.

i) Pyrene, ii) Cyclobutadiene, iii) Furan.
7. Arrange the increasing order of bond order of the following:
a) O2, O2-, O22-, O2+, O22+
b) He, He+
c) O2, N2, F2
8. What are the differences between n-type and p-type semiconductor?

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