Structure and Bonding

Core Chemistry 1A Dr. Andrew Hughes Lecture1

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Handout
Course synopsis Textbooks
Atkins & Shriver, Inorganic Chemistry Atkins & de Paula, Physical Chemistry Housecroft & Constable, Chemistry Winter, Chemical Bonding

Blank periodic table Problem sheet duo.dur.ac.uk

more support material model answers to questions from the problem sheet

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Lecture 1 - Outline
Introduction to the course
A2-level assumptions Overlap with Physics Mathematical knowledge assumed

Electron is a wave - Wave-particle duality The de Broglie relationship Schrdinger equation Electrons (waves) in 1 dimension - particle in a box Whats important? node - a point where = 0 Born interpretation of 2 as probability

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Structure and Bonding

Chemistry deals with the behaviour of the elements which make up the periodic table. We need to understand the atomic structure of these elements We need to understand how these elements come together to make molecules, compounds, etc. - chemical bonding Structure and Bonding can be highly mathematical - the approach of this lecture course will be deliberately to avoid Maths and explain everything with pictures where possible Do you not need to learn any of the little Maths that is presented. The picture is what is important. A more rigorous approach will be taken in 2nd year Chemistry
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Quantum Theory
Quantum Theory is the theory which describes the structure of atoms and molecules 1900-1925 - electron is a particle - Older Quantum Theory
Historically important Easier to understand particles But fails to explain many experimental observations

1925 - electron is a wave - wave mechanics

Explains everything Waves are harder to visualise

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Quantum Theory
verb - to quantize - to restrict a physical quantity to one of a fixed set of numbers noun - quantum - a naturally occurring fixed minimum of some entity such that all other amounts of that entity occurring in physical processes in nature are fixed multiples thereof. MONEY - all UK prices are quantized in terms of the penny
2.50 is sensible 10 p is sensible 1.387 p is NOT sensible

Quantum numbers = integers (usually)

1, 2, 3, 4, 5 . sometimes + or -

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Wave - particle duality

The solution is to treat electrons not as particles but as waves Experimental evidence
electrons can be diffracted by a crystal Davisson + Germer (1925) fired electrons at nickel X-rays can be diffracted by a crystal diffraction is a property of waves

By analogy - light has particle properties

light has momentum (photoelectric effect) light comes in quantized packets known as photons - particles of light

Mathematically we can treat electrons and light as particles or waves - as appropriate to the problem under discussion We just use particle maths or wave maths as necessary
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The de Broglie relation (1924)

de Broglie suggested that all matter has characteristics of both waves (wavelength ) and particles (momentum p = m x v) h = Planks constant = 6.63 x Js Short wavelength = high momentum Long wavelength = low momentum kinetic energy = curvature 10-34

h = mv

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Duality only matters for small particles

An electron accelerated through a potential of 100 V has a of 120 pm. Typical bond lengths in molecules are 100 pm. Electrons are diffracted by molecules

A tennis ball (m = 150 g) at 100 mph (45 ms-1)

h 6.63x10 34 = = 10 34 metres mv 0.15 45

This wavelength is very small, and we can expect little diffraction of a typical Greg Rusedski serve.
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Schrdinger Equation
This is a mathematical description of how a wave behaves in an energy field or force field It is the starting point of wave mechanics It cannot be deduced from classical mechanics, and cannot be proved, except that it correctly accounts for experiment It can get highly mathematical
2 x
2

2 y
2

2 z
2

8 2 m h
2

(E V ) = 0

We will just explore pictorially how waves behave Start in 1 dimension, then 2D and finally 3D (hydrogen)
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Electron waves in 1 dimension - 1

Sometimes known as a particle in a box An electron confined in a box of length L Potential energy = 0 inside box, at the walls Models the electronic structure of metals, and conjugated materials such as poly-acetylene

Macroscopic example = violin string

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Electron waves in 1 dimension - 2

The electron waves must satisfy certain conditions, the most important of which is that they are standing waves - they have zero amplitude (height) at the walls Hence only certain waves are allowed Half and full wavelengths wave height at point x = = wavefunction

nx n ( x ) = C sin L
n = 1, 2, 3, 4,. a quantum number 1 dimension, so 1 quantum number node is a point where (psi) = 0

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Electron waves in 1 dimension - 3

Energy of the wave is given by

E=

n 2h 2 8mL2

where n is the quantum number Hence energy is never zero - concept of zero-point energy Since is zero at the walls, but smooth, continuous and non-zero elsewhere, the wave must be curved curvature of is the kinetic energy

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Electron waves in 1 dimension - 4

E=

n 2h 2 8mL2

nx n ( x ) = C sin L

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Electron waves in 1 dimension - 5

Mathematical aside on this slide - NOT important Eigenfunctions = another name for allowed wavefunctions Wavefunctions corresponding to different energies are orthogonal, i.e., the integral of their product is 0 e.g.

x 3x 1 3 = sin sin dx = 0 L L

integral equals the total shaded area and is zero

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Summary of lecture 1
Electron is a wave - Wave-particle duality The de Broglie relationship Schrdinger equation Electrons (waves) in 1 dimension - particle in a box

Energy concept of zero-point energy nodes

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Textbook pages
Atkins & de Paula, Physical Chemistry, 7th ed. Chapter 11, pages 293 304 (bit advanced) Atkins & Shriver, Inorganic Chemistry, not much suitable, try pages 10 & 11 Housecroft and Constable, Chemistry, Chapter 2, pages 45 - 51 Mark Winter, Chemical Bonding, Chapter 1, pages 1 -9

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