The Pauli Exclusion Principle

See what happens when you click on lithium (Li)--

that's element number three in the periodic table.

There are three electrons, all right--but why is the

yellow one so much higher up on the chart? In the
picture, it looks like that one is a lot farther away from
the nucleus than the others...hey, does that mean it's in
a higher energy level?

Exactly. If you move the mouse over any electron

on the chart, you'll see a little blue number appear
above it. This tells you, in eV, how much energy it
would take to free that electron from the clutches of
the nucleus. In the case of the outermost electron, this is
called the ionization energy.

Hmm...the electrons in the lower row have higher

numbers listed. I guess that makes sense--the closer
they are to the nucleus, the more strongly the electric
force would be pulling them in. But that means the
electrons in higher energy levels have lower numbers on
the chart...

The terminology is a little confusing, I agree. Think

of it this way: the more energy of its own an electron
has, the less additional energy it needs in order to
escape.
Okay, so why is that third electron in a higher level
than the first two? Why not just add it to the lowest
one?

Because the lowest level is "full"; it can't hold more

than two electrons.

Why? That sounds totally arbitrary to me.

The rule that's operating here is called the Pauli

exclusion principle, first proposed by
Wolfgang Pauli. Pauli guessed that two
electrons can't be in the same "quantum state"--
I'll explain more fully what that means later. In this
context, it means that two identical electrons can't be in
the same energy level in the same atom.

But you just told me that the lowest energy level can
hold two electrons.
 Ah, yes--two electrons that are not identical. They
differ in a characteristic called spin...
Spin
Spin? What's that?

Well, it's an additional property that electrons

(and other particles) possess. Here's an
analogy: think about the Earth orbiting the
sun--

Haven't you just been pounding into my head that

electrons don't orbit like planets?

It's true, they don't--and yet that picture remains

helpful and illuminating in many contexts. So
bear with me for a moment: think about the Earth.
Not only does it orbit around the sun once a year,
it's also spinning once a day on its own axis...
 And that's what spin is! Although I suppose you're
going to tell me that electrons don't really spin, any
more than they really orbit.

You catch on quickly. They don't spin--but it's

tremendously useful to think about them as if they
did, and for most practical purposes, you can. In the
present case, think of the two electrons in that lowest
energy level as spinning in opposite directions. It's often
said that one has "spin up" and the other "spin down."

So each level has room for a spin up and a spin

down--that makes sense. But you haven't explained
s, p, and d yet; there must be more complications
to worry about.

Indeed...
Electron Configurations Continued
Take a look at the elements beyond lithium and see
what you can discover.

Let's see...the fourth element, beryllium (Be), has a

second electron in the higher energy level, which means
that level now has both a spin up and a spin down. So the
next element should begin a third energy level--is that
right?

See for yourself. Try clicking on boron (B), the fifth

element--you know, the one Bruce Willis was so
excited about.

Hey, what's going on? The fifth electron has a

slightly higher energy than the other yellow ones, but
it's not directly above them; it's in that column
labeled "p."

Ah. Do you have any ideas about what might be

happening?

Well...my best guess is that the colored rows,

pink and yellow, represent the main energy levels,
and s, p, and d are like smaller sublevels of them.

Very good. So what do you think is going to happen

as you keep going along that row of the periodic
table?

Hmm...carbon (C) has a second electron in the p

column, so now s and p in the yellow row each have
a spin up and a spin down. The next electron must
start a whole new energy level, or maybe it goes into the d
column, if that's the next higher sublevel.

Sounds very logical...but now look at nitrogen (N).

Hey, the seventh electron went into the p

column too! How can there be three with the
same energy?

It gets worse. Go on.

Oxygen (O), fluorine (F), neon (Ne)--more

electrons just keep getting stuffed into that
same state. What happened to the exclusion
principle? This makes no sense at all!

It makes perfect sense, once you know the rules.

Rules for Electron Configurations

I wish you'd stop being so mysterious and explain
these "rules" you keep referring to.

I was just about to do that. I have to warn you,

though, that the rules may seem arbitrary to you,
and I won't be giving any satisfactory explanation
of the reasons for them. Partly that's because I want to
spare you a lot of complicated math, and partly it's because
this is just the way nature is. I'll just ask you to have faith
that all this numerology comes out of a sophisticated
mathematical theory, and has been upheld time after time
by experiment.

I can, if you like, tell you about quantum

numbers; they provide a more quantitative
way of understanding these rules.

For now I think I'll be satisfied if you can tell me how

to predict those electron arrangements you've been
showing me.

I can do that.
First of all, you
were correct
when you
guessed that those
colored rows in the
chart correspond to the
"main energy levels";
they're often called
primary energy levels,
incidentally. Usually, a
higher row means a
higher energy, and energy gaps between rows tend to be
quite large, in comparison with the gap between, say, s and
p.

Are you ever going to explain what s and p mean?

I'll do that right now. As you surmised, the s, p,

and d columns represent smaller "sublevels" of the
primary rows...

Then why not just call them A, B, and C, or

something else at least vaguely logical?

This is a bit of archaic notation left

over from nineteenth century
spectroscopy--rather silly, but
everyone uses it, so we're stuck with
it. If you must know, s stands for "sharp," p is
for "principal," and d is for "diffuse"--
supposedly they refer to the appearance of
various spectral lines. The next one is called f,
for "fundamental"; mercifully, the subsequent
ones just go alphabetically: g, h, etc.
Electron Clouds and Energy Levels
Okay, so why is it that s only holds two
electrons, but p has room for six?

Well...remember that each electron is

existing in one of those strange probability clouds,
which, as you've seen, can have widely varying
shapes and sizes. Another statement of the Pauli
exclusion principle I mentioned is this: no two
electrons in an atom can be in the same type of cloud
with the same spin.

So you're saying that p electrons have more

cloud shapes available to them?

Precisely. It happens that s

clouds are always
spherical; the spheres just
get bigger as the primary
energy level increases.

However, p and d states are more interesting: there can be several different-shaped clouds
at the same energy. For example, here are two p states from the second primary level:
It turns out that there are three kinds of p clouds in each primary level.

...and each one can hold a spin up and a spin down, so that's why six electrons
fit into the p column!

Very good. You can think of each electron's "quantum state," its full,
unique description, as being the sum of a particular probability cloud plus a
spin:

A certain d state in the

spin down
third primary level

Futhermore, there are five different shapes for d (hence room for ten electrons),
and seven in the next sublevel, f...I hope you're noticing a pattern here. (If you
want to know more about where these numbers come from, go ask Dr. Mahan
about quantum numbers.)

Electron Configurations and the

Periodic Table
I understand the rules so far, but I
still have a lot of questions. First of
all, I can see from the chart that the
lowest row only has s electrons, but
the next row has electrons in both the
s level and the p level, or whatever
you're supposed to call them...

"Sublevel" is fine; you can also

speak of electrons' being in s or
p "states." You'll frequently
hear these states called
orbitals, especially in chemistry. Of
course, that term can be a little
confusing--

Yeah, yeah, I know--because

electrons don't really orbit.
 Good, you've been paying
attention. Incidentally, the s
states in the first primary level
are called 1s orbitals, those in the
second row 2s, and so forth.
Now, to return to your question:
another rule you'll have to remember
is that the number of sublevels
increases with each primary energy
level. The first row has just s orbitals,
the second has s and p, the third s, p,
and d, and so forth.

The way the periodic table is

arranged is starting to make
sense to me now. The rows of
the table match up with the
primary energy levels--that's why the
first row only has two elements. In
the second row, lithium and
beryllium are filling the two 2s spots;
then there's a big space because the
next six elements are filling the 2p
orbitals.
 That's exactly right. Now look
at the third row; is it the way
you'd expect it to be?

Hmm...sodium (Na) and

magnesium (Mg) add the two
3s electrons, and then the next
six elements, up to argon (Ar), fill the
3p orbitals. That's all fine, but why
does the row end there? This row
should have a d sublevel, too, if you
were telling the truth.

I never lie--but I won't deny

that there are more subtleties I
haven't yet revealed to you.
Click on potassium (K), the first
element in the fourth row.

Hey! Now there's an electron in

an 4s state, and still nothing in
the 3d orbitals. How do you
explain that?

Electron
Configuratio
ns and the
Periodic
 Table II
I've never
come right
out and said
this, but I'm sure
you've noticed that
the energy levels
get filled in order
from lowest
energy to highest;
when you add a
new electron, it
goes into the
lowest-energy
state that's
available.

Sure, that's
pretty
obvious.
That's why I
thought the next
electron for
potassium would
go into a d orbital
instead of up to a
whole new row--
you said that a
higher primary
level always
means a higher
energy.

said
usually,
not
always.
The
energy
levels
aren't
always so
well-
behaved
as one
might like;
it
sometimes
happens
that the
first
orbitals in
a "higher"
primary
level
actually
have less
energy
than the
top
orbitals of
the level
below.
Click on
the
advanced
button to
find out
why this
occurs.

So in

potassium, the 4s
orbitals end up
with less energy
than the 3d
states--that's why
potassium starts a
new row in the
periodic table. I
bet calcium (Ca)
puts an electron in
that second 4s
orbital...yup, it
does.

Okay, now
click on
scandium
(Sc).

Now the 3d
orbitals are
getting some
attention! All
those elements
from scandium
through zinc (Zn)
are just filling the
ten green d spaces.
Then gallium (Ga)
goes back up and
starts the 4p
orbital.

This
periodic
table ends
at krypton,
when the 4p
orbitals are filled--
but of course one
can keep going.
Click here to open
an extended
version of the
periodic table,
which shows the
electron
configurations for
the elements up to
103. I'll let you
play around with
this and figure out
the order in which
the various
orbitals are filled.
A note about the
arrangement of
elements: barium (Ba) is
element number 56;
element 57, lanthanum
(La), begins that first
separate row at the
bottom, which continues
up to number 71,
lutetium (Lu). Number
72, hafnium (Hf), is up
next to barium again. A
similar thing happens in
the seventh row of the
table. Look at the
electron configurations
and see if you can tell
why these elements are
arranged in this way.
 A Chemists' Perspective on the Periodic Table 1

All right, I think I understand now why

the periodic table is laid out the way it is.
The rows go with the primary energy
levels...
1
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
7
7
6
6
6
6
6
6
6
6
6
6
6
6
6
6
7
7
7
7
7
7
7
7
7
7
7
7
7
7
 ...and there are different sections of the table that go with the different sublevels.

That's right; you can think of the table as being divided into "blocks"
like this:

s s
s s p p p p p p
s s p p p p p p
s s d d d d d d d d d d p p p p p p
s s d d d d d d d d d d p p p p p p
s s d d d d d d d d d d p p p p p p
s s
f f f f f f f f f f f f f f
f f f f f f f f f f f f f f

That makes so much sense! Now I can see why someone had the idea of putting
the elements in a table like this; once you know how the electron configurations
work, this arrangement wouldn't be so hard to come up with.

Actually, the first designer of the periodic table knew nothing about
energy levels or even electrons; at the time, hardly anything was known
about the structure of atoms.

Really? Then how would anyone know which elements to put where?

Well, that's quite an interesting story. You see, there's more to the periodic
table than just electron configurations. Up until now I've been giving you a
physicist's view--from the bottom up, so to speak. Now we'll look at the
periodic table from a chemist's perspective, from the top down

The Origin of the Periodic Table

 I know what the periodic table looks like, but where
did it come from? Whose idea was it to arrange the
elements this way?

In 1869, a Russian chemist named Dmitri

Mendeleev came up with a way of organizing
the elements that were known at the time.
He set them out in order of atomic weight, and then
grouped them into rows and columns based on their
chemical and physical properties.

1869...that's way before the Schrödinger model, or

even the Rutherford model.

That's right. Mendeleev had no idea what atoms were

made of or why they behaved as they did.
Nevertheless, he was able to put together the
periodic table almost as we know it today--except that
some elements were missing, because they were unknown
in 1869.

Based on the gaps in his table, Mendeleev

even succeeded in predicting the existence
and properties of several new elements.

That's pretty impressive. Can you

tell me more about how
Mendeleev organized the table? What kinds
of properties did he use?

His basic rule was this: the elements in any column,

or group, of the table are similar to their column-
mates. For example, look at the first column on the
left, underneath hydrogen (H). The elements in this group
are called the alkali metals; they're all soft metals that
react violently with water to make hydrogen gas.
Click here if you'd like to read more about Mendeleev's
methods and the chemistry of his time
Periodic Properties
Hmm...so the elements in the table are
arranged in order from lightest to heaviest,
and elements in the same column have
matching properties. That's
right.

That means that elements whose atomic weights are

really close together can be very different, and some
elements with far-apart atomic weights are very
similar. As you move from lighter atoms to heavier
ones, you keep periodically running across the same
properties...

Hence the name

periodic table.

Oh, right.

I don't mean to pick on you; what you said was

actually a very important insight. The periodic table
is full of repeating patterns. Take atomic size, for
instance: atoms get bigger as you move down a
column, and smaller as you move to the right across a row,
or period.

That's so weird! I'd think the atoms would just get

bigger as they got heavier; why do they get smaller as
you move to the right?

The answer lies in the underlying structure of those

atoms...
Atomic Structure and Periodic Properties
I'll show you some of the details of atomic structure
using an interactive periodic table applet, which, I
hope, should now have opened in another window.

If you don't already have the periodic table applet open, click here:
to open it now.
 After Mendeleev's time, scientists discovered
what you already know: an atom consists of
a positively charged nucleus, made of
neutrons and protons, and some negatively
charged electrons swarming around it.

But what exactly is the configuration of those electrons?

That's the key to understanding why each element behaves
the way it does.

"Configuration"? I'm not sure I understand what that

means. Does it have something to do with that chart
in the applet, the one that says "s p d" at the top?

Yes; that chart shows how the electrons are arranged

in the selected element. I'd be happy to explain in
detail how the electrons organize themselves; if
you'd prefer, I can also give you a short crash course in
interpreting the chart.

Now that we've talked about the structure of atoms,

can you answer my question about their sizes?

There are two patterns to be explained: atoms get

bigger as you go down a group, and smaller as
you go to the right across a period. The reason for
the first one shouldn't be so hard to see now; look again
down the column of alkali metals in the applet.
 Each time you move down, you add another
primary level--lithium's highest electron is in a 2s
state, for sodium it's 3s, and so on.

Exactly. And the higher an electron's energy, the

farther from the nucleus it is.

So the atoms get bigger as you add electrons to

higher energy levels--that makes sense. But
why do they get smaller as you move to the right?

Well, you'll notice that within a period, the outermost

electrons are all in the same primary level--that is, at
(roughly) the same distance from the nucleus. But as
you move to the right, the elements increase in atomic
number; each element has one more proton than its left-
hand neighbor. The more protons in the nucleus, the more
strongly the valence electrons are pulled in...

...and so the atoms shrink! Also, I can see from the

chart that the ionization energies get larger as you
go to the right; that must be for the same reason.

Very good! Similarly, the ionization energies

decrease as you move down a group.
 Atomic Structure and Chemical Properties
You said that electron configurations are "the key to
understanding why each element behaves the way it
does." How does that work?

I'll give you an example: look again at that far left

group with hydrogen and the alkali metals. Start at
the top and go down, clicking on each element in
turn; what do you notice about the electrons?

Um...well, in each one of these, the very top electron

is starting a new colored row; it's all by itself in the s
sublevel.

Very good! The chart will tell you that

the ionization energy for that element is
quite small. It wouldn't take much to send
that one solitary electron sailing off into
dizzying freedom--and that sort of thing,
electrons leaving their home atoms, leads directly
to chemical reactions.

So that's why the alkali metals react

so violently--it's easy to set them
off.
 Atomic Structure and Chemical
Reactions
Do all elements lose their top
electrons in chemical reactions?

No; sometimes the opposite

happens. Take a look at the
second column from the right in
the periodic table--the one that
starts with fluorine (F).

These elements have their highest

electrons in p orbitals--five at the
same energy. p has room for six,
doesn't it?

That's right. These elements are

called the halogens; they're
highly reactive, too, but in a
different way than the alkali
metals. What sets them off is not losing
one of their own, but picking up a stray
electron, which fits perfectly into that
"empty space" in the p sublevel.

Wow, it sounds like the halogens

and the alkali metals would be
perfect for each other.
 You're absolutely right;
those two groups love to
form compounds together.
For example, I'm sure
you're familiar with sodium chloride,
NaCl.

What would the electrons look

like in an element that wasn't very
reactive?

Look at the far right group, with

helium (He) at the top.

Except for helium, all of these have

a "full" p sublevel at the top, with
six electrons.

Yes. Helium, of course, has a

"full" s sublevel--you may recall
 that the first primary level has
only s orbitals. These guys are
called the noble gases, and
they're perfectly happy with themselves
as they are--no desire to give up or take
in electrons. As a consequence, they
hardly ever form compounds with other
elements.

In general, the arrangement of the

outermost electrons, called valence
electrons, tells you all about an
element's chemical behavior.