Hunds Rule and Magnetism

This idea of spectroscopic notation can also help us explain a variety of different properties and
phenomena seen on the Periodic Table. One of these properties is the idea of magnetism. We
know that some metals respond to a magnetic field and others dont as well. Why is that? To
answer that question, we first need to understand what magnetism is.
Magnetism is an atoms response to a field applied to it. You should remember from Physics
class that a charged particle that spins produces a magnetic field. This is very much like the
earths magnetic field. Whichever way the particle spins, the field is generated in a particular
direction.

Here is a particle
that is spinning.
Because it is spinning this direction,
it generates a magnetic field like this:

Here is a particle
that is spinning in
the opposite direction. Its field is
reversed from the
first:

Lets set up an experiment. We will place a sample of an element on a scale and zero it with a
magnetic field off. The we will apply a magnetic field and see how much the sample is moved
by the magnetic field. The more it is moved, the greater the number on the scale.

Without getting to specific into the values, lets collect the data based upon the following scale:
Some response to a field

No response to a field

Lots of response to a field

Lets then apply the experiment to all the elements in the fourth row of the periodic table. Here
are the results:

Ca

Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

Ga

Ge

As

Se

Br

Kr

Doesnt seem like much of a pattern but lets look at with the splits for each subshell shown:

Ca

Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

Ga

Ge

As

Se

Br

Kr

A couple of things to notice here. First of all, it seems within each subshell, response to a magnetic field starts off small and then gradually increases until the halfway at which point it goes
back down. Second, at the end of every subshell the response is zero:

Ca

Sc

Ti

Increases to
halfway

Cr

Mn

Fe

Co

Ni

Cu

Zn

Ga

After halfway
decreases until
zero at the end

Ge

As

Increases to
halfway

Se

Br

Kr

After halfway
decreases until
zero at the end

When we combine all the knowledge from our previous sections and apply it to this, we can
begin to make some sense of the above results. Lets do it section by section:

Ca

For potassium, K, the spectroscopic notation is [Ar] 4s 1 which means there is one electron in
the s orbital. Because this is the s subshell, l=0
Thus, ml can only = 0 which means there is only 1 orbital.
Lets represent this orbital with a box:

n=4
l=0
ml = 0

Now what we have to do is fill that orbital with the proper number of electrons. Since potassium is 4s 1, we have
only 1 electron that must have ms = +1/2 or 1/2. It doesnt matter which you choose. Lets represent +1/2 with
an up arrow and 1/2 with a down arrow. Lets start with +1/2 or the up arrow in the orbital box:
s

n=4
l=0
ml = 0
ms = +1/2

What we see is that there is one electron in the box spinning up and making a magnetic field. Thus, we get a
small response to the applied field which explains the results seen at the top of the page.

Ca

Now lets move on to Calcium. Ca is [Ar] 4s2. This means it has 2 electrons in the 4s subshell.
The Pauli Exclusion Principle says that no 2 electrons can have the exact same four quantum
numbers so the 2 electrons in calcium must be:
n=4
l=0
ml = 0
ms = +1/2

n=4
l=0
ml = 0
ms = -1/2

Which means that both these electrons are in the same orbital but they must be spinning in opposite directions. To
fill the orbital box we get:
n=4
l=0
ml = 0
ms = +1/2

n=4
l=0
ml = 0
ms = -1/2

What we see now is there are 2 electrons with opposite fields spinning in the same location.

The opposite nature of these resultant magnetic fields cancels each other out. Thus, Calcium exhibits no response
to a magnetic field which is exactly what we see on the results. The two results here are typical of what we see in a
variety of different elements so we need terms to identify them. The two terms are as follows:

Paramagnetic = the element responds to a magnetic field due to

unpaired electrons in orbitals
And
Diamagnetic = the element shows no response to a magnetic
field due to completely filled orbitals with no unpaired electrons
s
K
Ca

One unpaired electron so we see

a small response to magnetism

No unpaired electrons so we see

zero response to magnetism
Ca

Lets continue this across the row. Scandium is our next element
K

Ca

Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

Sc has the notation: [Ar] 4s23d1 which means its valence electrons are in the 3d subshell. Thus:
3d
n=3
l=2
ml = -2 -1 0 +1 +2
which means there are 5 orbitals which means we need to draw 5 orbital boxes past the s:
s

We know the 2 electrons in the 4s will cancel out their magnetic fields from having a full orbital box and the third electron will go into a d orbital unpaired which gives a small response
to a magnetic field:
s
2

Sc: [Ar] 4s 3d

Sc

All is following the pattern seen but were going to run into a question on the next element, Titanium. Doing the same thing as above, we have 2 choices. We either pair up this next electron
s

d
Paired electrons
in the d2 orbitals

Ti: [Ar] 4s23d2

OR we can put the next electron in the next orbital over:
s

Ti: [Ar] 4s23d2

d
2 electrons now unpaired in 2 different
orbitals

What do we choose? What would be the consequences of each and how would we know?
Think about the magnetism:

If we go with choice #1 which is that the next electron pairs up, what would be the expected
result for the magnetic field?
s

d
Paired electrons
in the d2 orbitals

Ti: [Ar] 4s23d2

Since all the electrons are paired, the response should be zero. Is that what we see?

Ca

Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

NO! In fact, the response Titanium has is MORE than that of Scandium which means it must
have more than 1 electron that is unpaired AND that unpaired electron must be spinning the
same way as to increase the magnetic field seen:
s

Ti: [Ar] 4s23d2

Both of these electrons are unpaired and spinning the same direction, thus giving off the same
magnetic field. Instead of canceling out, they
constructively interfere with each other and
boost the response to the magnetic field!

This trend continues across the row with the next three elements as we see the new electrons
being put in empty orbitals spinning the same direction and increasing the magnetism:
s

Sc: [Ar] 4s23d1

Ti: [Ar] 4s23d2
V: [Ar] 4s23d3
Cr: [Ar] 4s23d4
Mn: [Ar] 4s23d5

We see an increase in the number of unpaired

electrons all spinning the same direction and this
coincides with an appropriate increase in the
response to the magnetic field!

What we glean from this is what is known as Hunds Rule which says:
The most stable arrangement of electrons in an atom is when degenerate (same subshell) orbitals are half-filled spinning the same direction or totally filled.
Thus, we half-fill similar orbitals with electrons before we totally fill any of them. If we continue the pattern from before, however, we have to move past the point where all the d orbitals
are half-filled:
s

Sc: [Ar] 4s23d1

Ti: [Ar] 4s23d2
V: [Ar] 4s23d3
Cr: [Ar] 4s23d4

Working up to
half-filled

Increasing
magnetism

Must start filling the orbitals

with electrons
spinning the
other direction

Decreasing
magnetism

Mn: [Ar] 4s23d5

Fe: [Ar] 4s23d6
Co: [Ar] 4s23d7
2

Ni: [Ar] 4s 3d

Cu: [Ar] 4s23d9

Zn: [Ar] 4s23d10

And we must start filling the orbitals with electrons spinning the other direction. Every one of
these we add, the opposite magnetic field cancels out some the magnetic response. By the time
we get to Zinc, at the end of the subshell, all the orbitals are completely filled and thus Zn atoms are completely diamagnetic and give no response to magnetism.

This however, leads to two different exceptions that take place. I said before that Chromium
and Copper have the following arrangements:
s

Cr: [Ar] 4s23d4

Cu: [Ar] 4s23d9
This is, in fact, NOT true. Look at each notation and remember Hunds Rule (the most stable
arrangement is when similar orbitals are 1/2 filled or totally filled). In the case of Chromium,
four of the five degenerate orbitals are half-filled. In the case of Copper, all the degenerate d
orbitals are almost totally filled. The atom could gain extra stability if it just had one more electron to put in each. However, these are both metals; they dont like to gain electrons, they like
to lose them.
Because these orbitals overlap in energy and to gain extra stability, Chromium and Copper each
shift one electron from the s into the d:
s

Cr: [Ar] 4s23d4

Cu: [Ar] 4s23d9

Check out what just happened. Now each of the d orbitals are all satisfying Hunds Rule.
They are either half-filled spinning the same direction or totally filled. Thus the true spectroscopic notation of Chromium and Copper are:
s

Cr: [Ar] 4s13d5

Cu: [Ar] 4s13d10
There are many different elements that do this. However, these are the only two examples the
AP test people want you to know so they are the only ones we are going to focus on.