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ATOMIC ORBITALS

This page explains what atomic orbitals are in a way that makes
them understandable for introductory courses such as UK A level
and its equivalents. It explores s and p orbitals in some detail,
including their shapes and energies. d orbitals are described only in
terms of their energy, and f orbitals only get a passing mention.

What is an atomic orbital?


Orbitals and orbits
When a planet moves around the sun, you can plot a definite path
for it which is called an orbit. A simple view of the atom looks
similar and you may have pictured the electrons as orbiting around
the nucleus. The truth is different, and electrons in fact inhabit
regions of space known as orbitals.
Orbits and orbitals sound similar, but they have quite different
meanings. It is essential that you understand the difference
between them.
The impossibility of drawing orbits for electrons
To plot a path for something you need to know exactly where the
object is and be able to work out exactly where it's going to be an
instant later. You can't do this for electrons.
The Heisenberg Uncertainty Principle says - loosely - that you
can't know with certainty both where an electron is and where it's
going next. (What it actually says is that it is impossible to define
with absolute precision, at the same time, both the position and the
momentum of an electron.)
That makes it impossible to plot an orbit for an electron around a
nucleus. Is this a big problem? No. If something is impossible, you

have to accept it and find a way around it.


Note: Over the years I have had a steady drip of questions
from students in which it is obvious that they still think of
electrons as orbiting around a nucleus - which is completely
wrong! I have added a page about why the idea of orbits is
wrong to try to avoid having to say the same thing over and
over again!

Hydrogen's electron - the 1s orbital


Note: In this diagram (and the orbital diagrams that follow),
the nucleus is shown very much larger than it really is. This is
just for clarity.

Suppose you had a single hydrogen atom and at a particular


instant plotted the position of the one electron. Soon afterwards,
you do the same thing, and find that it is in a new position. You
have no idea how it got from the first place to the
second.
You keep on doing this over and over again, and
gradually build up a sort of 3D map of the places
that the electron is likely to be found.
In the hydrogen case, the electron can be found anywhere within a
spherical space surrounding the nucleus. The diagram shows
across-section through this spherical space.
95% of the time (or any other percentage you choose), the electron
will be found within a fairly easily defined region of space quite
close to the nucleus. Such a region of space is called
an orbital.You can think of an orbital as being the region of space
in which the electron lives.
Note: If you wanted to be absolutely 100% sure of where the
electron is, you would have to draw an orbital the size of the

Universe!

What is the electron doing in the orbital? We don't know, we can't


know, and so we just ignore the problem! All you can say is that if
an electron is in a particular orbital it will have a particular definable
energy.
Each orbital has a name.
The orbital occupied by the hydrogen electron is called a 1s
orbital. The "1" represents the fact that the orbital is in the energy
level closest to the nucleus. The "s" tells you about the shape of
the orbital. s orbitals are spherically symmetric around the nucleus in each case, like a hollow ball made of rather chunky material with
the nucleus at its centre.
The orbital on the left is a 2s orbital.This is similar to a 1s orbital
except that the region where there is the greatest chance of finding
the electron is further from the nucleus - this is an orbital at the
second energy level.
If you look carefully, you will notice that there
is another region of slightly higher electron
density (where the dots are thicker) nearer
the nucleus. ("Electron density" is another
way of talking about how likely you are to
find an electron at a particular place.)
2s (and 3s, 4s, etc) electrons spend some of their time closer to the
nucleus than you might expect. The effect of this is to slightly
reduce the energy of electrons in s orbitals. The nearer the nucleus
the electrons get, the lower their energy.
3s, 4s (etc) orbitals get progressively further from the nucleus.
p orbitals
Not all electrons inhabit s orbitals (in fact, very few electrons live in
s orbitals). At the first energy level, the only orbital available to
electrons is the 1s orbital, but at the second level, as well as a 2s

orbital, there are also orbitals called 2p orbitals.


A p orbital is rather like 2 identical balloons tied
together at the nucleus. The diagram on the left is a
cross-section through that 3-dimensional region of
space. Once again, the orbital shows where there
is a 95% chance of finding a particular electron.

Taking chemistry further: If you imagine a horizontal plane


through the nucleus, with one lobe of the orbital above the
plane and the other beneath it, there is a zero probability of
finding the electron on that plane. So how does the electron get
from one lobe to the other if it can never pass through the
plane of the nucleus? At this introductory level you just have to
accept that it does! If you want to find out more, read about the
wave nature of electrons.

Unlike an s orbital, a p orbital points in a particular direction - the


one drawn points up and down the page.
At any one energy level it is possible to have three absolutely
equivalent p orbitals pointing mutually at right angles to each other.
These are arbitrarily given the symbols px, py and pz. This is simply
for convenience - what you might think of as the x, y or z direction
changes constantly as the atom tumbles in space.
The p orbitals at the second energy level are called 2p x, 2py and
2pz. There are similar orbitals at subsequent
levels - 3px, 3py, 3pz, 4px, 4py, 4pz and so on.
All levels except for the first level have p
orbitals. At the higher levels the lobes get
more elongated, with the most likely place to
find the electron more distant from the
nucleus.

d and f orbitals
In addition to s and p orbitals, there are two other sets of orbitals
which become available for electrons to inhabit at higher energy
levels. At the third level, there is a set of five d orbitals (with
complicated shapes and names) as well as the 3s and 3p orbitals
(3px, 3py, 3pz). At the third level there are a total of nine orbitals
altogether.
At the fourth level, as well the 4s and 4p and 4d orbitals there are
an additional seven f orbitals - 16 orbitals in all. s, p, d and f orbitals
are then available at all higher energy levels as well.
For the moment, you need to be aware that there are sets of five d
orbitals at levels from the third level upwards, but you probably
won't be expected to draw them or name them. Apart from a
passing reference, you won't come across f orbitals at all.
Note: Some UK-based syllabuses will eventually want you to
be able to draw, or at least recognise, the shapes of d orbitals.
I am not including them now because I don't want to add
confusion to what is already a difficult introductory topic. Check
your syllabus and past papers to find out what you need to
know. If you are a studying a UK-based syllabus and haven't
got these, follow this link to find out how to get hold of them.

Fitting electrons into orbitals


You can think of an atom as a very bizarre house (like an inverted
pyramid!) - with the nucleus living on the ground floor, and then
various rooms (orbitals) on the higher floors occupied by the
electrons. On the first floor there is only 1 room (the 1s orbital); on
the second floor there are 4 rooms (the 2s, 2px, 2py and
2pzorbitals); on the third floor there are 9 rooms (one 3s orbital,
three 3p orbitals and five 3d orbitals); and so on. But the rooms
aren't very big . . . Each orbital can only hold 2 electrons.
A convenient way of showing the orbitals that the electrons live in is

to draw "electrons-in-boxes".
"Electrons-in-boxes"
Orbitals can be represented as boxes with the electrons in them
shown as arrows. Often an up-arrow and a down-arrow are used to
show that the electrons are in some way different.
Taking chemistry further: The need to have all electrons in
an atom different comes out of quantum theory. If they live in
different orbitals, that's fine - but if they are both in the same
orbital there has to be some subtle distinction between them.
Quantum theory allocates them a property known as "spin" which is what the arrows are intended to suggest.

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