SHRI VISHNU ENGINEERING COLLEGE FOR WOMEN::BHIMAVARAM

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ACADEMIC YEAR: 23-24

CHEMISTRY
UNIT-1: STRUCTURE AND BONDING MODELS

What Is Molecular Orbital Theory?

The molecular orbital theory (often abbreviated to MOT) is a theory on chemical bonding developed at
the beginning of the twentieth century by F. Hund and R. S. Mulliken to describe the structure and
properties of different molecules. The valence-bond theory failed to adequately explain how certain
molecules contain two or more equivalent bonds whose bond orders lie between that of a single bond
and that of a double bond, such as the bonds in resonance-stabilised molecules. This is where the
molecular orbital theory proved to be more powerful than the valence-bond theory (since the orbitals
described by the MOT reflect the geometries of the molecules to which it is applied).

Types of Molecular Orbitals

According to the molecular orbital theory, there are two types of primary molecular orbitals which are
formed due to the linear combination of atomic orbitals. These orbitals are mentioned below.

1. Bonding Molecular Orbital

This is the type of molecular orbital that is formed by the addition of overlapping an atomic orbital.
Bonding Molecular Orbital is indicated by the addition of wave function indicating any molecular
orbital. This type of molecular orbital shows the least relative energy which implies that the orbital
energy of the resultant orbital is always lower than that of the bonding species. The reason behind this is
that the nuclei of both the sharing electrons show more attraction.

2. Anti Bonding Molecular Orbitals

In anti bonding molecular orbital, the electron density of the two bonding atoms is concentrated behind
the nuclei. As a result, the distance between the nuclei of the two atoms increases. The anti-bonding
molecular orbital weakens the bonds between two atoms.

The type of molecular orbital is opposite to that of bonding molecular orbital as it is formed when the
overlapping atomic orbital is subtracted. It is formed by subtraction of wave function. So, the energy of
the orbital that is formed after bonding is always higher than that of the parent orbital. This also implies
that the relative energy of the anti-bonding orbital is always greater. The reason behind this is that the
nuclei of the sharing electrons repulse each other.

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M.O.D of O2

M.O.D of N2

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M.O.D of CO

M.O.D of NO

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Pi Molecular Orbitals of Butadiene
The Butadienyl Pi System (n = 4)
As the name suggests, butadiene is composed of 4 carbons with two adjacent pi bonds. As we showed
in this earlier post on conjugation and resonance, 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.
Using the principles we learned from drawing out the pi molecular orbitals of the allyl system, let’s try
to draw out what each of these four molecular orbitals should look like.

The Lowest-Energy Molecular Orbital (π1)

The lowest energy molecular orbital will have p orbitals with phases in complete alignment with each
other. This is very easy to draw: just draw four consecutive p-orbitals all aligned the same way.

We could have also drawn the pi-system with all the shaded lobes pointing up: it’s the same thing. The
constructive overlap between the lobes results in a pi orbital that extends over the entire length of the pi
system (above right); there are zero nodes between the p orbitals themselves. A physical interpretation of
this orbital is that an electron in this orbital is delocalized over the length of the pi system.

The Highest-Energy Molecular Orbital (π4)

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The highest-energy molecular orbital is also very easy to draw. Just draw n (4 in our case) p orbitals and
alternate the phases of each. This creates a pi system with three nodes (areas where the lobes change
sign). We’ve drawn the nodes in as red dotted lines.

The Second Lowest-Energy Molecular Orbital (π2)

The second lowest-energy molecular orbital in butadiene will have 1 node. The trick is knowing where
to put it.

As we saw with the allyl system, the node cannot just be placed anywhere; the mathematical properties
of the Schrödinger wave equation (which we don’t need to get into) dictate its position. Thankfully,
node placement for this orbital is pretty straightforward: just plunk it in the middle. (This goes for all
systems with a single node, by the way).

Note how the phases flip in the centre of the pi orbital. This corresponds to the situation we’d expect to
see for two adjacent non-interacting pi bonds, where the electrons are each confined to pi orbitals
spanning two carbons each, with a node in the middle (above right).

The Third Lowest-Energy Molecular Orbital (π3)

Finally, we come to the third lowest-energy molecular orbital (or second highest, if you prefer). This has
two nodes.

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Where to place them?

The general principle is that they are placed symmetrically with respect to the centre. This is what the
orbital picture looks like:

This gives us a 2-carbon pi orbital in the centre flanked by two one-carbon orbitals on the sides.

The Molecular Orbital Diagram for the Butadienyl System (n=4)

Now that we have all the pieces, all we need to do to construct the molecular orbital diagram for the
butadienyl system is to arrange the orbitals in order of increasing energy. That gives us the following
figure (note that we haven’t added any electrons to it yet).

A molecular orbital diagram without electrons is like an apartment building without people. So, let’s
pick the simplest possible molecule to apply to this system: butadiene.

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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’ve highlighted two molecular orbitals on this diagram as being of particular interest, because, as
we’ll see, they’re where the action usually happens. The are sometimes called the “frontier” orbitals.

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 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.
We’ll have more to say about the HOMO and LUMO shortly, but that’s sufficient for now.

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The Molecular Orbitals of Benzene

A molecular orbital description of benzene provides a more satisfying and more general treatment of
"aromaticity". We know that benzene has a planar hexagonal structure in which all the carbon atoms are
sp2 hybridized, and all the carbon-carbon bonds are equal in length. As shown below, the remaining
cyclic array of six p-orbitals (one on each carbon) overlap to generate six molecular orbitals, three
bonding and three anti bonding. The plus and minus signs shown in the diagram do not represent
electrostatic charge but refer to phase signs in the equations that describe these orbitals (in the diagram
the phases are also color coded). When the phases correspond, the orbitals overlap to generate a
common region of like phase, with those orbitals having the greatest overlap (e.g. π1) being lowest in
energy. The remaining carbon valence electrons then occupy these molecular orbitals in pairs, resulting
in a fully occupied (6 electrons) set of bonding molecular orbitals. It is this completely filled set of
bonding orbitals, or closed shell, that gives the benzene ring its thermodynamic and chemical stability,
just as a filled valence shell octet confers stability on the inert gases.

Schrödinger Equation

Time-dependent Schrödinger Wave Equation derivation is provided here so that students can learn the
concept more effectively.

Questions related to the derivation of the Schrödinger Wave Equation are one of the most commonly asked
questions in board exams and various competitive exams. The derivation of the Schrödinger Wave
Equation is given below in such a way that students understand the concept in an interesting and easy
manner. Schrödinger Equation is a mathematical expression which describes the change of a physical
quantity over time in which the quantum effects like wave-particle duality are significant. The
Schrödinger Equation has two forms: the time-dependent Schrödinger Equation and the time-
independent Schrödinger Equation. The time-dependent Schrödinger Wave Equation derivation is
provided here so that students can learn the concept more effectively.

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Questions related to the derivation of the Schrödinger Wave Equation are one of the most commonly
asked questions in board exams and various competitive exams. The derivation of the Schrödinger Wave
Equation is given below in such a way that students understand the concept in an interesting and easy
manner.

Schrödinger Equation is a mathematical expression which describes the change of a physical quantity
over time in which the quantum effects like wave-particle duality are significant. The Schrödinger
Equation has two forms: the time-dependent Schrödinger Equation and the time-independent
Schrödinger Equation. The

What Is Schrodinger Wave Equation?

The Schrodinger wave equation is a mathematical expression describing the energy and position of the
electron in space and time, taking into account the matter wave nature of the electron inside an atom.

It is based on three considerations. They are

 Classical plane wave equation

 Broglie’s hypothesis of matter-wave
 Conservation of energy
The Schrodinger equation gives us a detailed account of the form of the wave functions or probability
waves that control the motion of some smaller particles. The equation also describes how these waves
are influenced by external factors. Moreover, the equation makes use of the energy conservation concept
that offers details about the behaviour of an electron that is attached to the nucleus.

Besides, by calculating the Schrödinger equation, we obtain Ψ and Ψ2, which helps us determine the
quantum numbers, as well as the orientations and the shape of orbitals, where electrons are found in a
molecule or an atom.

There are two equations, which are a time-dependent Schrödinger equation and a time-independent
Schrödinger equation.

The time-dependent Schrödinger equation is represented as

OR
The time-dependent Schrödinger equation in position basis is given as
Where,
i = Imaginary unit, Ψ = Time-dependent wavefunction, h2 is h-bar, V(x) = potential and
Also Read: Quantum Mechanical Model of Atom

The time-independent Schrödinger equation in compressed form can be expressed as

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The time-independent-Schrödinger-nonrelativistic-equation

Schrodinger Wave Equation Derivation

Classical Plane Wave Equation

A wave is a disturbance of a physical quantity undergoing simple harmonic motion or oscillations about its
place. The disturbance gets passed on to its neighbours in a sinusoidal form.

What Is Schrodinger Wave Equation?

The Schrodinger wave equation is a mathematical expression describing the energy and position of the
electron in space and time, taking into account the matter wave nature of the electron inside an atom.

It is based on three considerations. They are

 Classical plane wave equation

 Broglie’s hypothesis of matter-wave
 Conservation of energy
The Schrodinger equation gives us a detailed account of the form of the wave functions or probability waves
that control the motion of some smaller particles. The equation also describes how these waves are
influenced by external factors. Moreover, the equation makes use of the energy conservation concept that
offers details about the behaviour of an electron that is attached to the nucleus.

Besides, by calculating the Schrödinger equation, we obtain Ψ and Ψ2, which helps us determine the
quantum numbers, as well as the orientations and the shape of orbitals, where electrons are found in a
molecule or an atom.

Schrodinger Wave Equation Derivation Time independent wave equation

The total energy is the sum of the kinetic and potential energy of the particle.

E = KE + PE

The equation is also written as

where,
The Schrodinger equation is written as HΨ = EΨ, where h is said to be a Hamiltonian operator.

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Schrodinger wave equation for particle in One Dimensional Box:

A simple classical example is a particle in a one-dimension box within infinitely repulsive barriers.

In this case, the value of equals zero for and infinite in the walls. The wave function beyond the
walls of the box is null. The wave function and energies of the particle inside the box are obtained by
the solution of SE with reported in the central part of Figure 1.

Derivation of the wavefunction

The one-dimension SE is a linear second-order differential equation with solutions

using the Euler relation

we can write
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or called and we can write

by substituting in SE with (e.g. particle inside the box)

we obtain

that gives

the quantised total energy of the system.

Now we estimate the values of constant k, C, and D of the solution.

By applying the boundary conditions

we obtain for x=0 that

It is more convenient to represent the parameter k as a circular frequency with the De Broglie’s
wavelength of the particle

For x=L the solution gives

This is accomplished for or

and

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We still need to calculate the value of the constant C. As the square of the wave function gives the
probability density and the integral the probability of finding a particle in a region of the box, then if we
integrate over all the x-axis, the probability should be equal to one:

(1)

Using this integral we can find the value of C that normalize the function. The integral
with can be calculated by part

as with in this case

therefore

so we have that

taking the last integral in the second member of the equation to the first member we have

but the first term in the second member is equal to zero and the second equal to L, hence

Therefore from Equ. (1), we have

and .

Therefore the wavefunctions of a particle in a box are given by

and the associated energies are

The quantum number n is an integer associated with the different energy levels of the particle. Larger n
values correspond to higher energy levels of the system. Also, note in the graphs the increase in the
number of nodes in the wave function with the increase of the value of n.

In Figure 2, the wavefunctions for the first three energy level of the particle in a box are shown.

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The separation between the adjacent energy level with quantum number $n$ and $n+1$ is

The probability density for a particle in a box is given by the square of the wavefunction as follows

and the probability to find the particle in a region of the box can be calculated using the
following integral

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