CHE-10047

CHEMICAL CONCEPTS AND STRUCTURE

ELECTRONS IN ATOMS LECTURES 1-2
2011-2012
Dr David J McGarvey

TOWARDS A MORE SOPHISTICATED

VIEW OF CHEMICAL BONDING
Recall that we asked which of the following is the correct
shape for allene?
trigonal planar
linear epg
epg & mg
& mg
H
H
?

H2C C CH2
ALLENE

C C C

H
H
H

H
H
C C C
H

To answer this question (and others) we need to develop our

understanding of chemical bonding to a higher level of
sophistication; this requires us to start with a detailed
examination of the properties of electrons in atoms.

ELECTRONS IN ATOMS
An understanding of the electronic structure of atoms is
fundamental to a deeper understanding of the chemical and
spectroscopic behaviour of the elements and the compounds
they form.
The purpose of this section is to understand how electrons are
arranged within neutral and ionised atoms.

We can then use this knowledge base to explore more

sophisticated models of chemical bonding in the next section.

Chapters 2, (11, 16)

Chapter 1

Chapter 4

LEARNING OUTCOMES
Apply the Rydberg equation to predict the positions of spectral
lines for hydrogenic atoms.
Define and classify atomic orbitals in terms of the quantum
numbers (n, l , ml) and the nomenclature s, p, d, f etc
Relate properties of atomic orbitals (e.g. energy, shape,
directional) to the quantum numbers n, l , ml
Determine permitted values for l and ml for a given value of n
Sketch the shapes (boundary surfaces) of s, 2p and 3d-orbitals
with reference to x, y, z axes.

ELECTRONS IN ATOMS
Here is a familiar cartoon of electrons in an atom:

But it isnt like this! The reality is much more complex!

The behaviour of electrons in atoms can be derived and
described using quantum mechanics (QM).
At this stage we are not going to be concerned with the
mathematical aspects of QM, but we will study in detail the
results and concepts yielded by the applications of QM to
electrons in atoms.

TWO IMPORTANT FEATURES

OF THE QUANTUM WORLD
In classical systems (described by Newtons laws) the position
of an object can be specified exactly.
In quantum systems, we can only talk about the probability of a
particle being at a particular location: some regions have higher
probability, and some lower.

Chemical Structure and Reactivity: an Integrated Approach, James Keeler and Peter Wothers, OUP 2008

TWO IMPORTANT FEATURES

OF THE QUANTUM WORLD
In classical systems which is what we
experience directly in our day-to-day lives
energy can vary smoothly from one value to
another.
In quantum systems, which applies to very
small particles, the energy can only have
certain values, called energy levels.
We can see direct evidence of this if we look
at the light emitted from a hydrogen or neon
discharge lamp.

Chemical Structure and Reactivity: an Integrated Approach, James Keeler and Peter Wothers, OUP 2008

THE HYDROGEN ATOM SPECTRUM

http://jersey.uoregon.edu/vlab/elements/Elements.html

THE HYDROGEN ATOM

The hydrogen atom consists of a proton and an electron.
The energy of the electron is restricted to certain values; i.e. its
energy is quantised.
For current purposes we can visualise the electron as being able to
occupy orbits specified by a quantum number n, which is
restricted to integral values:
n = 1, 2, 3, 4, .....
It is also customary to refer to
shells (e.g. the n = 1 shell).
The higher the value of n, the
higher the energy.
http://www.nobeliefs.com/atom.htm

THE ORIGIN OF EMISSION LINES IN

THE HYDROGEN ATOM SPECTRUM
n = 32

n = 42

n = 52

http://www.nobeliefs.com/atom.htm

THE HYDROGEN ATOM SPECTRUM

Atomic spectroscopy forms the basis of some

exceptionally sensitive and selective analytical
techniques (Atomic Absorption Spectroscopy (AAS),
Inductively Coupled Plasma Atomic Emission
Spectroscopy (ICP-AES))
Shriver & Atkins 2009

ATOMIC SPECTRA, ENERGY LEVELS & LIGHT

E h h

hc

Atkins and Jones 2005

When an electron in an atom undergoes a

transition from a higher energy level to a
lower one, it loses energy by emitting a
photon.
Chemical Structure and Reactivity: an Integrated Approach, James Keeler and Peter Wothers, OUP 2008

Self-Test: Calculate the energy (in kJ mol-1) associated with

blue light of wavelength 400 nm.

Avogadro constant

NA = 6.022 x 1023 mol-1

Planck constant

h = 6.626 x 10-34 J s

Velocity of light (vacuum)

c = 2.998 x 108 m s-1

nanometre

nm = 10-9 m

THE HYDROGEN ATOM SPECTRUM

AND THE RYDBERG EQUATION
1890: Rydberg noticed that all lines in the hydrogen atom emission spectrum
fit a general empirical equation.

1
1
RH 2 2
nL nU

L lower U upper

nL=2
nL=3
nL=4

RH
9

RH
4

nL=1

Atkins & Jones 2009

RH

Chemical Structure and Reactivity: an Integrated

Approach, James Keeler and Peter Wothers, OUP 2008

Self-Test: Calculate (in nm) for the transition from nU = 3 nL = 2.

Rydberg constant

RH = 1.09737 x 105 cm-1

1
1
RH 2 2
nL nU

L lower U upper

THEORY AND EXPERIMENT

The pattern of lines in the H-atom spectrum is an experimental
observation.
The Rydberg formula is empirical.
But is there a theory that could be used to predict the behaviour
of the electron in the H-atom and hence predict its spectrum?
The answer, of course, is yes; Quantum Mechanics and the
Schrdinger equation.
The possible energies of an electron in an H-atom (energy
levels) and its associated spatial properties can be determined
by solving an equation called the Schrdinger equation.

THE SCHRDINGER EQUATION FOR THE

HYDROGEN ATOM CAN BE SOLVED EXACTLY
The key feature of the Schrdinger equation is its
solution, the wavefunction ().
For the electron in a hydrogen atom, the
wavefunctions are known as atomic orbitals.
The atomic orbitals can only be viable (acceptable) if
the energy is quantised.
The result is the following expression for the energy of the electron
in the hydrogen atom:

RH
En 2
n

n 1, 2, 3,...

We say that the energy is quantised and each energy level has an
associated quantum number, n, which affects its energy. The value
of the Rydberg constant RH arises naturally from the theory!

THE SCHRDINGER EQUATION FOR THE

HYDROGEN ATOM CAN BE SOLVED EXACTLY
More generally, for hydrogenic
atoms (an atom with 1
electron) of atomic number Z,
the energy of the electron in the
atom is given by:

RH Z
En 2
n
n 1, 2, 3,...

An example of a hydrogenic
atom is He+ (Z=2)

RH

RH
9

RH
4

RH

4 RH

THE SCHRDINGER EQUATION FOR THE

HYDROGEN ATOM CAN BE SOLVED EXACTLY
Overall, the atomic orbitals require the specification of three quantum numbers:
n, l, ml.
n = principal quantum number - energy.
l = angular momentum quantum number - shape.

l=0

l=2

l=1

ml = magnetic quantum number direction.

ml=0

ml=+1

ml=-1

Chemical Structure and Reactivity: an Integrated Approach, James Keeler and Peter Wothers, OUP 2008

HYDROGENIC ATOMIC ORBITALS

The possible values of the quantum numbers are interconnected
such that the value of n determines the possible values of l and
hence ml.

n 1, 2, 3,....
l 0,1, 2,...(n 1)
ml l , l 1, l 2... l

l=0
l=1
l=2
l=3
l=4

s-orbital
p-orbital
d-orbital
f-orbital
g-orbital

For hydrogenic atoms (i.e., one electron atoms), orbitals with

the same value of n are degenerate; i.e. of equal energy.

n 1, 2, 3,....
l 0,1, 2,...(n 1)
ml l , l 1, l 2... l

l=0
l=1
l=2
l=3
l=4

s-orbital
p-orbital
d-orbital
f-orbital
g-orbital

HYDROGENIC ATOMIC ORBITALS

The number of possible orbitals for a specified value of n is
equal to n2
The value of n gives the number of types of orbital (subshells).
For example, for n=3, there are 9 orbitals and 3 types of orbital
(i.e. three subshells):

Types of orbital: 3s, 3p & 3d

For hydrogenic atoms, the energy only depends on one
quantum number: n
i.e. for a hydrogenic atom, the energy of 2s = 2p and the
energy of 3s = 3p = 3d.

Self-Test: How many orbitals are there with n=4? What orbitals
correspond to (i) n=5, l=2, (ii) n=4, l=3? What are n, l and the
possible values of ml for 5p orbitals?

HYDROGENIC ATOMIC ORBITALS

Atkins & Jones 2009

Self-Test: Complete the following table

n
1
5
3
6
4

l
0
3
1
0
2

ml values

Orbital name

BOUNDARY SURFACE
REPRESENTATIONS: 2s & 2p-ORBITALS
A boundary surface representation of an orbital is a surface within
which there is typically a 95% probability of finding the electron.

Different shades reflect different sign of . Red is +ve and blue

is ve. The sign of has nothing to do with charge.
Chemical Structure and Reactivity: an Integrated Approach, James Keeler and Peter Wothers, OUP 2008

BOUNDARY SURFACE
REPRESENTATIONS: 3p-ORBITALS
Notice that the general shape is similar to the 2p orbitals see
later!

Chemical Structure and Reactivity: an Integrated Approach, James Keeler and Peter Wothers, OUP 2008

BOUNDARY SURFACE
REPRESENTATIONS: 3d-ORBITALS

Chemical Structure and Reactivity: an Integrated Approach, James Keeler and Peter Wothers, OUP 2008

BOUNDARY SURFACE
REPRESENTATIONS: 4f-ORBITALS

Chemical Structure and Reactivity: an Integrated Approach, James Keeler and Peter Wothers, OUP 2008