Elements, Atoms

and The Periodic Table

L4: The shape of atoms

Dr Daniel J Price
The structure of atoms
Electrons have wave-like properties!
This wave-like property is represented by the ‘wavefunction’, y
Schrodinger’s equation allows us to calculate the shape of the allowed
wavefunctions, and it also connects each wavefunction with an associated energy for that function.

The wavefunction is a function

y(x,y,z)
The wavefunction emerges naturally as a solution to the Schrodinger equation,
along with an associated energy E.

These wavefunctions turn out to be the ‘atomic orbitals’

Labelling the wavefunctions
We can identify and label the different solutions to Schrodinger’s equation by a series of quantum numbers

Electrons in orbitals are fully characterized by Four quantum numbers

n, l, ml and ms
We use the values of n, l, and ml as
labels for the different wavefunctions

We have already met n, the principal quantum number

In Bohr’s model it defines how far the electron is from the nucleus
n = 1, 2, 3, 4, 5 . . . . . .
 The larger the value of n and the greater

The Principle quantum number, n the potential energy, the radius and size

Bohr’s atom
n determines the size of an orbit

n=5 n=6
n=4
Lyman
n = 3 series
Balmer
n=2
series

n=1
Principle quantum number and the periods
Main

As you go down a group the size increases significantly and across a period it decreases by a small amount.
The angular momentum quantum number, l
l defines the radial spatial distribution of the wavefunction
Allowed values of l are limited by the value of n
Values l = 0, 1, 2, … (n-1)
defines the shape of an orbital

Allowed values of n and l Traditionally use letters

to represent l
n = 1, l = 0
l=0 s-orbital
n = 2, l = 0 or 1
l=1 p-orbital
n = 3, l = 0 or 1 or 2
l=2 d-orbital
n = 4, l = 0 or 1 or 2 or 3
l=3 f-orbital
… …
The first orbital: n = 1, l = 0 (s) First wavefunction is represented with the greek letter
si. Simplest of any orbitals.

Probability amplitude of the first

wavefunction y n = 1, l = 0
1s
1. The value is positive everywhere
2. It is highest at the nucleus
3. It approaches zero as we move away
from the nucleus
4. It is spherically symmetric
So this is what the 1 s wavefunction
looks like. It’s very difficult to show. Psi
Py2 High
1 s gives values for
different coordinates in space,
different, x, y, z coordinates.
The vales are always positive, it is
lowest, meaning close to zero far
from the centre. And it reaches its
highest value at the nucleus.

What is the probability, P, of finding the

electron in the finite element dx dy dz ?

y
square the wavefunction for ^the box
probability
1. The value is positive everywhere
2. There is no edge to the atom
3. The highest chance of finding the
electron is at the centre Low
Also this probability gradually decays – asymotopically to zero – so it never actually reaches zero as we move away from the nucleus.
How big is the first orbital? How big is an atom?
1s-orbital (n = 1, l = 0) Surface enclosing
99% probability
of finding the
electron.
sphere

The orbit is a cloud of electron density, it is helpful to construct a boundary surface

Here size depends on our chosen probability; 90%, 99%, 99.9%, 100% is infinitely big!
How big is the first orbital?
What is the probability of finding
the electron at radius r?from the nucleus
What is the
r probability of
finding electron
Dr in shell, with
volume Dr ?
Volume enclosed by a shell of
thickness Dr, is proportional to r2
Peak maximum
“Average” distance from nucleus
We need to sample
with a finite-element to obtain a
meaningful probability. So imagine a
shell, of radius r, and thickness
delta r. Actually, the volume of such an
element increases as r squared r
increases. That is the
volume gets bigger at a faster rate than
the radius gets bigger
“Atomic radius”
The second orbital: n = 2, l = 0 (s)
y2s n = 2, l = 0
Positive

1. The value is positive and negative

2. There is a sphere where the y = 0
3. It approaches zero as we move away
from the nucleus.
4. It is spherically symmetric zero
Probability
Py2
1. The value is positive everywhere
2. There is a sphere where P = 0
3. There is no edge to the atom negative
4. It is spherically symmetric Probability amplitude
The shapes of s-orbitals
n = 1, l = 0 n = 2, l = 0 n = 3, l = 0
y1s y2s y3s

The second point is that although we have changes in

the structure of the wavefunction in the inner part of the orbitals, this is mostly incidental.
How an atom reacts or interacts with others is mostly dependent upon the outermost
part of the atom

1s-orbital 2s-orbital 3s-orbital

What about l = 1? (p-orbitals)
y2p n = 2, l = 1
z-axis
Positive
1. The value is positive and negative
2.
3.
There is a plane where the y = 0
It is 0 at the nucleus
Probability
4. It approaches zero as we move
zero
away from the nucleus
The nodal plane passes right
through the
nucleus. So unlike s-orbitals, there is

Py2 zero chance of finding an electron in

a p-orbital at the atomic
nucleus.

1. The value is positive everywhere

2. There is a plane where the y = 0
3. It has two lobes (dumbbell Probability negative
shaped)
– directed along an axis amplitude
The magnetic quantum number, ml
ml defines the orientation of the wavefunction
Allowed values of ml are limited by the value of l
Values ml = -l, -l+1, -l+2, ….., +l
Each of
these possible values of ml is another solution to Schrodinger’s equation.
That is another orbital.
Allowed values of l and ml How many orbitals?
l = 0, ml = 0 one s-orbital
l = 1, ml = -1 or 0 or +1 three p-orbitals
l = 2, ml = -2 or -1 or 0 or +1 or +2 five d-orbitals
l = 3, ml = -3 or -2 or -1 or 0 or +1 or +2 or +3 seven f-orbitals
… … …. …..
The three p-orbitals: l = 1; ml = -1, 0, +1
Q.N. Wavefunction Type of value
n=2
Y2p- 2px-orbital
y2px
l =1 complex numbers
z = (a + bi)
ml = -1 We’ve already met the middle one here, where ml equals zero. But for the plus and the minus, the wavefunction is a bit more
complicated, by which I mean complex, in the mathematical sense. I mean each point in space is characterised by a real and an
imaginary component. There is a mathematical trick; the psi 2 p
zero is aligned along the z-axis, and we can relabel this as the psi 2 p z orbital. The two complex functions can be
n=2
y2p0
combined in such a way to eliminate the imaginary component, producing a px and a py orbital.
So together for l = 1 we have a set of three orbitals, with lobes, each directed along the x-axis, the yaxis, and the z-axis.

l =1 positive and negative 2py-orbital

ml = 0 y2py
n=2
l =1 Y2p+ complex numbers
2pz-orbital
y2pz
z = (a + bi)
ml = +1
The three p-orbitals: l = 1; ml = -1, 0, +1
Most easily visualised with a boundary surface:
e.g. enclosing a 99% probability of finding the electron

Degenerate orbitals: Same energy, orthogonal functions

The shapes of p-orbitals
n = 2, l = 1, ml = 0 n = 3, l = 1, ml = 0 n = 4, l = 1, ml = 0
2pz 3pz 4pz
z
Like the s-orbitals, it is their shape and
the character of the outer parts of these atoms that is similar throughout, and
this is in part
responsible for their characteristic chemistry.

x
The shapes of all orbitals Looking at the maximum value of l for each allowed value of n,
clearly reveals some patterns in the shapes of these orbitals. The
1s had no nodal plane, the 2p has
one nodal plane, the 3d orbitals, when l = 2 have two nodal planes,
and the 4f orbitals have three
nodal planes.

n=1 n=2 n=3 n=4

l =0 l =1 l =2 l =3
3d 4f
1s 2p

= node P = 0
The five d-orbitals: l = 2; ml = -2, -1, 0, +1, +2
In fact we need to do the same sort of trick with the l = 2 orbital solutions. Where we take some
combination of the mathematically complex function, to eliminate the imaginary components, and
get the following 5 d-orbitals.
n = 1 l = 0 ml = 0 1s 1 orbital n = 4 l = 0 ml = 0 4s 1 orbital
l = 1 ml = -1
n = 2 l = 0 ml = 0 3 orbitals
2s 1 orbital ml = 0 4p
l = 1 ml = -1 ml = +1
ml = 0 2p 3 orbitals l = 2 ml = -2
ml = +1 ml = -1
n = 3 l = 0 ml = 0 3s 1 orbital
ml = 0 4d 5 orbitals
ml = +1
l = 1 ml = -1
3 orbitals ml = +2
ml = 0 3p l = 3 ml = -3
ml = +1
ml = -2
l = 2 ml = -2
ml = -1
ml = -1
ml = 0 4f 7 orbitals
ml = 0 3d 5 orbitals ml = +1
ml = +1
ml = +2
ml = +2
ml = +3
Energy levels (Hydrogen only)
Schrödinger equation gives y’s, with energies E(y)

5s 5p 5d 5f
4s 4p 4d 4f
3s 3p 3d
When there is only 1 electron, as in the case of thy hydrogen atom, or any
hydrogenic ion, such as
2s 2p He+, then the energy of a wavefunction depends only on the value of n.
Here the energy of the 2s
and the 2p orbits are exactly the same. We can put the electron for the
hydrogen atom in any of the
orbitals, but clearly the lowest energy, the most stable, or the ground state
1s configuration, is
obtained by putting the electron in the lowest available orbit.

When only 1 interaction (nucleus – electron), the energy is determined by n only.

e.g. E(y2s ) = E(y2p)
Shells, sub-shells, blocks and orbitals
Looks like 2 electrons per orbital
1 orbital
3 orbitals

5 orbitals

7 orbitals

Since each sequential atom has 1 more electron, it really looks like you can get two electrons in any
one orbital.
 Pauli exclusion principle
Fundamental Property of electrons,
they cannot occupy the same space.

Only 2 electrons can occupy any one orbital

S is very much like l, and has a related quantum number called m subscript s. The M subscript s

Wolfgang Pauli follows the same rules on what values it can take, it depend upon the value of s, and ranges from –
s to +s, going up in integer units.

In the case of an electron, s is one half. That means that ms can only take values of minus one half,
or plus one half. These define the orientation of the electrons spin angular momentum, put simply,
whether it is spin up, or spin down.
The spin quantum number, ms
Electrons have a spin
quantum number, s
s is an angular momentum, like l it has
an associated ms quantum number

Allowed values of ms are limited

by the value of s
Values ms = -s, -s+1, -s+2, ….., +s

For electrons s = ½
therefore ms = -½ or +½
ms defines spin orientation
The thing about electrons
No two electrons in the same atom can have
all 4 quantum numbers same
The size, shape and orientation of an orbital are defined by the 3 quantum numbers;
n, l and ml no 2 electrons
in an atom, can have the same set of values
for their quantum numbers. But each orbital
The spin orientation of an electron is defined by the 1 quantum number;
can take up
to 2 electrons. So the options are it can be
ms empty, and have no electrons in it. It can be
half-filled
with one electron in it, or it can be filled with
exactly 2 electrons, each with opposite spin
For electrons ms can only take 2 values;
orientations

ms = +½ (spin up) or ms = -½ (spin down)

So only 2 electrons can occupy any one orbital

End