SCHROEDINGER’S QUANTUM ATOMIC MODEL

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. 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.

QUANTUM NUMBERS AND ATOMIC ORBITALS

The wave function Ψ developed by Schroedinger allows the calculation of the different
energetic levels and the probability of locating the electron in the hydrogen atom (Ψ 2
gives the so called probability density). The electron will have just some discrete
(discontinuous) energetic values determined by a set of whole numbers called the
quantum numbers n, l and m. Each set of three quantum numbers define what is called
an orbital (a particular solution of the equation) that is, the energetic state and the zone
where the electron will very probably be located. The principal quantum number n is
related to the size of the zone where the probability of finding the electron is relevant
(higher than 99%). Its possible values are 1, 2, 3,… and so on. The values for the
secondary quantum number (azimuthal) l range from 0 to n – 1. It gives information
about the symmetry of the zone: l = 0 describes for each level a spherically symmetric
zone (called the “s” sub-level) l =1 defines a second and slightly more energetic sub-
level called the “p” sub-level, a zone showing cylindrical symmetry, shaped as two
tangent spherical lobes and with a particular feature: the probability of finding the
electron at the plane at which both zones “touch” is zero. For l = 3 the orbital (“d”
orbital) shows two of these planes perpendicular to each other that give it a four-leaf-
clover shape. For higher values of l (the “f” orbitals with three restriction planes) the
shapes become more complicated.
The third quantum number is called m the magnetic quantum number and can have
values from zero to ± l. It gives the possible orientation of the orbitals. There is one
possible orientation for an s orbital (l = 1) because in that case the only possible value of
m is m= 0. For the p sublevel three values are possible for m, namely 0, +1 and – 1.
Therefore there are three possible p orbitals centred each along one of the axes x, y or z.

1
The orientations for the five d orbitals and the seven “f” orbitals are difficult to
describe.
A summary of the foregoing ideas is shown
1st level n = 1 l = 0 m= 0 (the only 1s
orbital)
2nd level n = 2 l = 0 m = 0 (the only 2s
orbital)
l = 1 m = 0 m = +1 m=-1 (the three 2p
orbitals)
3rd level n = 3 l = 0 m = 0 (the only 3s
orbital)
l=1 m=0 m=+1 m=-1 (the three 3p
orbitals)
1=2 m=0 m=+1 m = + 2 m = - 1 m = -2 (the five 3d
orbitals) and so on.

HYDROGEN'S ELECTRON

The 1s orbital

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 a cross-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.
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.)
3s, 4s (etc) orbitals get progressively further from the nucleus.

2
p orbitals

Not all orbitals are s orbitals. At the first energy level, the only orbital
available 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 right is a cross-section through that 3-
dimensional region of space. Once again, the orbital shows where there
is a 95% chance of finding the electron.

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 2px, 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 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 (3p x, 3py, 3pz). At the
third level there is 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.
Apart from a passing reference, you won't come across f orbitals at all.

The electron in a hydrogen atom will be at its lowest possible energetic level that is, the
1s orbital. But if it is given energy (excited) it will jump up to any of the other levels
and fall or cascade down to its original state emitting light. The calculated energy
differences for these possible “fall downs” coincides within the experimental error with
the observed emissions of the hydrogen atom. This confirms and supports Schrödinger’s
studies.

POLIELECTRONIC ATOMS

Now what for more than one electron? The problem cannot be solved exactly but can be
approached better and better by means of the perturbation treatment (corrections on the
unperturbed or simple model). Results agree reasonably with experimental data.
The orbitals for complex atoms are similar to those of the hydrogen atom’s but because
of the multiplicity of electrons shielding effects appear (an inner electron shields or

3
protects the outer electrons from the nuclear attraction). That causes some inter - level
crossing and consequently 3d orbitals are more energetic than 4s.
How are electrons located in complex atoms? There are three principles to be followed
when determining the electron distribution for an atom.

The construction principle (aufbau): electrons will occupy the lowest energetic level
available. Thus, electrons will accommodate as long as they can in the first level, then
in the second one and so on. But where is the limit? When does an orbital get to a “no
vacancies” state? Before we go to the second principle we will introduce a new quantum
number called the spin quantum number

Spin Quantum Number

There is a fourth quantum number not for the orbitals but a quantum number that
describes the electron itself. It is called the spin quantum number s and it stands for
the fact that electrons “seem” to behave as spinning tops. Some electrons are right
handed other electrons are left handed. Thus the spin quantum number shows only two
possible values: ± ½.

The exclusion (Pauli’s) principle: Not two electrons in an atom can have the same set
of four quantum numbers (this has to do with the identity of the particles). This answers
the question of a previous paragraph: there can be no more than two electrons per
orbital and in this case they should be “paired” that is show opposite spins. Were it
not so, two electrons would have identical sets of quantum numbers and Pauli’s
exclusion principle forbids it. That is why the first level (shell in elementary chemistry)
holds just two electrons: the orbital is the 1s orbital (n = 1, l = 0 and m = 0) so it can
accommodate no more than two electrons that should have opposite spins. How many
electrons can be accommodated in the second level?

The maximum multiplicity principle (Hund’s rule): when a sublevel is being filled,
electrons will be placed in different orbitals of the sublevel as long as they can. This
means that if three electrons have to be accommodated in a p sub level they will half
occupy each of the orbitals. This filling of orbitals singly where possible, only applies
where the orbitals have exactly the same energies (as with p orbitals, for example), and
helps to minimise the repulsions between electrons and so makes the atom more stable.
A fourth electron will have to be placed in one of the previously semi - occupied p
levels.

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 2pz orbitals); 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. (Pauli’s
exclusion principle).

4
The order of filling orbitals

Electrons fill low energy orbitals (closer to the nucleus) before they fill higher energy
ones. Where there is a choice between orbitals of equal energy, they fill the orbitals
singly as far as possible.
The diagram (not to scale) summarises the energies of the orbitals up to the 4p level.

Notice that the s orbital always has a slightly lower energy than the p orbitals at the
same energy level, so the s orbital always fills with electrons before the corresponding p
orbitals.
The real oddity is the position of the 3d orbitals. They are at a slightly higher level than
the 4s - and so it is the 4s orbital which will fill first, followed by all the 3d orbitals and
then the 4p orbitals. Similar confusion occurs at higher levels, with so much overlap
between the energy levels that the 4f orbitals don't fill until after the 6s, for example.
Knowing
All this seems quite difficult to handle but a diagram of Hund’s makes it very simple:
you just have to enter the diagram from the first corner, go straight through it and then
enter the second corner, go through, enter third corner etc. Every time you get to a
sublevel fill it before going to the next one. A worked example will be enough to make
things clear.

Suppose you are asked for the

electron configuration for
element number 17 (Cl). Its 17
electrons are going to be
distributed this way:
1- Enter at a: you stop at 1s and
put 2 electrons in it. You follow
the arrow and are out of the
diagram.
2- Go to b. You get to level 2s
and accommodate other 2
electrons. You follow the arrow
and you go out of the diagram.
3- Go to c. You get to level 2p
and accommodate other 6
electrons.
4-Insofar you have “used 10 electrons” Follow the arrow and you get to 3s. There
you accommodate 2 electrons.

5
 5- You follow the arrow and go out of the diagram. Go to d. You get to the 3p
sublevel where you can accommodate up to 6 electrons. But you just have 5
electrons, so you stop there.
6- The distribution will be: 1s2 2s2 2p6 3s2 3p5. Your atom has seven
electrons in its outer shell (3s and 3p) so it belongs to the seventh group of the
third period.

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.
A 1s orbital holding 2 electrons would be drawn as shown on the right, but it can be
written even more quickly as 1s2. This is read as "one s two" - not as "one s squared".
You mustn't confuse the two numbers in this notation:

The example given for oxygen will suffice for showing how to do it

1s2 2s2 2px2 2py1 2pz1

The last electron entered (with opposite spin) the 2px orbital; previously the other two p
orbitals were half – filled according to Hund’s rule.

Relating orbital filling to the Periodic Table

The first period

Hydrogen has its only electron in the 1s orbital - 1s1, and at helium the first level is
completely full - 1s2.

The second period

Now we need to start filling the second level, and hence start the second period.
Lithium's electron goes into the 2s orbital because that has a lower energy than the 2p
orbitals. Lithium has an electronic structure of 1s22s1. Beryllium adds a second electron
to this same level - 1s22s2.
Now the 2p levels start to fill. These levels all have the same energy, and so the
electrons go in singly at first.

6
 B 1s22s22px1
C 1s22s22px12py1
N 1s22s22px12py12pz1

The next electrons to go in will have to pair up with those already there.
O 1s22s22px22py12pz1
F 1s22s22px22py22pz1
Ne 1s22s22px22py22pz2
You can see that it is going to get progressively tedious to write the full electronic
structures of atoms as the number of electrons increases. There are two ways around
this, and you must be familiar with both.
Shortcut 1: All the various p electrons can be lumped together. For example, fluorine
could be written as 1s22s22p5, and neon as 1s22s22p6.
This is what is normally done if the electrons are in an inner layer. If the electrons are in
the bonding level (those on the outside of the atom), they are sometimes written in
shorthand, sometimes in full.
Shortcut 2: You can lump all the inner electrons together using, for example, the
symbol [Ne]. In this context, [Ne] means the electronic structure of neon - in other
words: 1s22s22px22py22pz2 You wouldn't do this with helium because it takes longer to
write [He] than it does 1s2.
On this basis the structure of chlorine would be written [Ne]3s23px23py23pz1.

The third period

At neon, all the second level orbitals are full, and so after this we have to start the third
period with sodium. The pattern of filling is now exactly the same as in the previous
period, except that everything is now happening at the 3-level.
For example: short version
Mg 1s22s22p63s2 [Ne]3s2
S 1s22s22p63s23px23py13pz1 [Ne]3s23px23py13pz1
Ar 1s22s22p63s23px23py23pz2 [Ne]3s23px23py23pz2

The beginning of the fourth period

At this point the 3-level orbitals aren't all full - the 3d levels haven't been used yet. But
if you refer back to the energies of the orbitals, you will see that the next lowest energy
orbital is the 4s - so that fills next.
K 1s22s22p63s23p64s1
Ca 1s22s22p63s23p64s2
There is strong evidence for this in the similarities in the chemistry of elements like
sodium (1s22s22p63s1) and potassium (1s22s22p63s23p64s1)
The outer electron governs their properties and that electron is in the same sort of orbital
in both of the elements. That wouldn't be true if the outer electron in potassium was 3d1.

BLOCKS

s- and p-block elements

7
The elements in group 1 of the Periodic Table all have an outer electronic structure of
ns1 (where n is a number between 2 and 7). All group 2 elements have an outer
electronic structure of ns2. Elements in groups 1 and 2 are described as s-block
elements. Elements from group 3 across to the noble gases all have their outer electrons
in p orbitals. These are then described as p-block elements.

d-block elements

Remember that the 4s orbital has

a lower energy than the 3d
orbitals and so fills first. Once
the 3d orbitals have filled up, the
next electrons go into the 4p
orbitals as you would expect.
d-block elements are elements in
which the last electron to be
added to the atom is in a d
orbital.
d electrons are almost always described as, for example, d5 or d8 - and not written as
separate orbitals. Remember that there are five d orbitals, and that the electrons will
inhabit them singly as far as possible. Up to 5 electrons will occupy orbitals on their
own. After that they will have to pair up.

d5 means

d8 means

Notice that all the 3-level orbitals are written together, even though the 3d electrons are
added to the atom after the 4s.

Now you can see what happens with the transition elements. When you have to
accommodate 21 electrons, the first 20 of them go to 1s2 2s2 2p6 3s2 3p6 4s2. But the 21st
electron will not go to the 4p sublevel but will enter the totally empty 3d sublevel that
because of inter level crossing is more energetic than 4s and has not been yet
occupied!!. There are 10 empty places to fill with electrons before proceeding to the 4p
sublevel: these elements with 2 electrons in their outer shells (4s) are very similar and
having just two electrons they will behave as metals. The differences among them come
from an inner sub shell that is being filled.

PROBLEMS ON SCHRÖDINGER’S MODEL

1- Explain what properties of an orbital can be related to each of the quantum

numbers

2- What is the spin quantum number?

3- Which of the following sets of quantum numbers are possible for two electrons
in an atom? Explain why the others can’t.
a- n=1 l=1 m=0 s=+1/2 and n=1 l=1 m=0 s=-1/2

8
 b- n=2 l=0 m=+1 s=-1/2 and n=2 l=0 m=+1 s=+1/2
c- n=2 l=1 m=0 s=-1/2 and n=2 l=1 m=0 s= -1/2
d- n=3 l=2 m=-2 s=+1/2 and n=3 l=2 m=-2 s=-1/2
e- Which of them are s, p or d electrons?

4- Using Hund’s diagram, find the electron configuration for the following atoms.
Find their atomic numbers in a periodic table. Use quantum boxes for
representing the configurations of N and Br.

N F Ar Ca Fe Br Ce U

5- The differential electron is the last one to be added to a configuration. Explain

why properties change so little when an electron is added to a Ce atom and so
much when added to an O atom.