MODULE

Molecular Orbital (MO) Theory

Topic 1: Electrons in Atoms

Felipe Garcia (Assistant Professor)

CY1101: Principles of Modern Chemistry

School of Physical and Mathematical Sciences, NTU

 Learning Objectives

By the end of this lecture, you will be able to:

Interpret atomic quantum numbers

Recognise wavefunctions and their angular and radial parts
Define radial distribution function (RDF)
Construct an RDF from a wavefunction graphically
Represent s, p and d orbital graphically

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 Atomic Orbitals
Orbitals and Quantum Numbers: Electrons in atoms occupy different orbitals (imagined as a specific energy level).

For example,

1s orbital two electrons

Any given orbital can only
2s orbital two electrons accommodate two electrons.

2p orbitals (px, py and pz) two electrons respectively

3d orbitals (dxy, dxy, dyz, dx2-y2 and dz2)

7f-orbitals.

Orbitals that have the same energy are described as degenerate.

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 Atomic Orbitals
Quantum Numbers and Their Properties

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 Atomic Orbitals
Generally, there is no need to specify ms (the spin) since it is the same for all electrons (ms =1/2).

No orbital (defined by its quantum numbers n, l, and ml) may contain more than two electrons. When there are
two, they only differ on their opposing spins (ms = +1/2 and ms = −1/2).

Any electron in an atom has a unique set of four quantum numbers. This is one form of the Pauli Principle.

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 Wavefunctions
A function is a mathematical tool into which we can feed a number to derive a new value.

The properties of an electron can be described by a mathematical function called wave function (ψ). This function
depends on n, l and ml. Hence, every electron is defined by n, l and ml.

Ψn,l ,ml (x,y,z)

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 Wavefunctions
The wave function can also be represented in polar coordinates (r, θ, ϕ) rather than Cartesian coordinates (x, y, z).

One of the advantages of polar coordinates over Cartesian coordinates is that the wave function ψ can be written
as the product two functions, 0 ≤ q ≤ p and 0 ≤ f ≤ 2p.

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 Wavefunctions
The angular function is determined by the quantum number l and ml.

shape of the orbitals orientation of the orbital in the space

The different shading of the lobes represents different signs of the wave function ψ.

Useful to know the sign for qualitative bonding purposes

The radial function is determined by the quantum numbers n and l.

Describes the electron density at different distances from the nucleus

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 Hydrogen Atom Wave Functions: Radial Functions

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 Hydrogen Atom Wave Functions: Angular Functions

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 The Radial Distribution Function (RDF)
A common way of representing the orbitals graphically is by showing the probability of finding an electron at a
given distance (electron density at a set distance), r (distance from the nucleus), summed over all angles (θ and φ).

This function is called the Radial Distribution Function (RDF) or radial probability function.

Interpreted as the total electron density in a thin shell at a distance (r) from the nucleus.

The RDF helps show which orbitals are most likely to be involved in reactions.

RDF = [Rn,l(r)]2 x 4pr2

[Rn,l(r)] is the radial part of the wavefunction

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 The Radial Distribution Function (RDF)

EXAMPLE

Compare the radial wave function (Rn,l(r), left) and RDF (RDF = [Rn,l(r)]2 x 4pr2, right) for 1s electrons. Radial
distribution functions and radial wave functions for 1s, 2s, 2p, 3s, 3p and 3d orbitals are shown below:

Rn,l(r) RDF = [Rn,l(r)]2 x 4pr2,

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 Wave Function Nodes
The sign of the wave function changes from positive to negative as it crosses the x-axis (there is a point at which
ψ=0). Such a position is called a node.

TOTAL NUMBER OF NODES = n-1

Number of angular noder = l
Number of radial nodes = n-l-1

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 3D Representation of the Orbitals
A wave function has a value at any point in the space. So for better understanding for the value at any given q, f
and r, 3D plots are extremely useful.

s-orbitals

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 3D Representation of the Orbitals

p-orbitals

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 3D Representation of the Orbitals

d-orbitals

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 3D Representation of the Orbitals

f-orbitals

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 Summary

The principal quantum number (n) describes the size of the orbital.

The angular quantum number (l) describes the shape of the orbital.

The magnetic quantum number (m), describes the orientation in space of a particular orbital.

Generally, there is no need to specify ms (the spin) since it is the same for all electrons (ms =1/2).

Any electron in an atom has a unique set of four quantum numbers.

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 Summary

Each wavefunction has two parts the radial part which changes with distance from the nucleus and an angular part
whose changes correspond to different shapes.

SIZE is determined by Rnl(r) = radial part of the wave function.

SHAPE determined by Yl,ml+ (q,f).

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 Summary

The Radial Distribution Function (RDF) represents the probability of finding an electron at a given distance from
the nucleus (r), summed over all angles (θ and φ).

RDF = [Rn,l(r)]2 x 4pr2

A node is a point at which ψ=0.

TOTAL NUMBER OF NODES = n-1

Number of angular nodes = l
Number of radial nodes = n-l-1

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 Summary

Orbital shapes are

s p

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 Contact Details

Email : Fgarcia@ntu.edu.sg
Office: CBC-05-19

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