Quantum Numbers and Atomic Orbitals

By solving the Schrdinger equation (H = E), we obtain a set of mathematical equations,

called wave functions (), which describe the probability of finding electrons at certain energy
levels within an atom.
A wave function for an electron in an atom is called an atomic orbital; this atomic orbital
describes a region of space in which there is a high probability of finding the electron. Energy
changes within an atom are the result of an electron changing from a wave pattern with one
energy to a wave pattern with a different energy (usually accompanied by the absorption or
emission of a photon of light).
Each electron in an atom is described by four different quantum numbers. The first three
(n, l, ml) specify the particular orbital of interest, and the fourth (ms) specifies how many
electrons can occupy that orbital.

1. Principal Quantum Number (n): n = 1, 2, 3, ,

Specifies the energy of an electron and the size of the orbital (the distance from the
nucleus of the peak in a radial probability distribution plot). All orbitals that have the
same value of n are said to be in the same shell (level). For a hydrogen atom with n=1,
the electron is in its ground state; if the electron is in the n=2 orbital, it is in an excited
state. The total number of orbitals for a given n value is n2.

2. Angular Momentum (Secondary, Azimunthal) Quantum Number (l): l = 0, ..., n-1.

Specifies the shape of an orbital with a particular principal quantum number. The
secondary quantum number divides the shells into smaller groups of orbitals
called subshells (sublevels). Usually, a letter code is used to identify l to avoid confusion
with n:
l
Letter

0
s

1
p

2
d

3
f

4
g

5
h

...
...

The subshell with n=2 and l=1 is the 2p subshell; if n=3 and l=0, it is the 3s subshell, and so on.
The value of l also has a slight effect on the energy of the subshell; the energy of the subshell
increases with l (s < p < d < f).

3. Magnetic Quantum Number (ml): ml = -l, ..., 0, ..., +l.

Specifies the orientation in space of an orbital of a given energy (n) and shape (l). This
number divides the subshell into individual orbitals which hold the electrons; there are

2l+1 orbitals in each subshell. Thus the s subshell has only one orbital, the p subshell has
three orbitals, and so on.

4. Spin Quantum Number (ms): ms = + or -.

Specifies the orientation of the spin axis of an electron. An electron can spin in only one
of two directions (sometimes called up and down).
The Pauli exclusion principle (Wolfgang Pauli, Nobel Prize 1945) states that no two
electrons in the same atom can have identical values for all four of their quantum
numbers. What this means is that no more than two electrons can occupy the same
orbital, and that two electrons in the same orbital must have opposite spins.
Because an electron spins, it creates a magnetic field, which can be oriented in one of two
directions. For two electrons in the same orbital, the spins must be opposite to each other;
the spins are said to be paired. These substances are not attracted to magnets and are said
to be diamagnetic. Atoms with more electrons that spin in one direction than another
contain unpaired electrons. These substances are weakly attracted to magnets and are
said to be paramagnetic.

Table of Allowed Quantum Numbers

n
1
2
3

l
0
0
1
0
1
2
0
1
2
3

ml
0
0
-1, 0, +1
0
-1, 0, +1
-2, -1, 0, +1, +2
0
-1, 0, +1
-2, -1, 0, +1, +2
-3, -2, -1, 0, +1, +2, +3

Number of
orbitals
1
1
3
1
3
5
1
3
5
7

Orbital
Name
1s
2s
2p
3s
3p
3d
4s
4p
4d
4f

Number of
electrons
2
2
6
2
6
10
2
6
10
14

In a ground state configuration, all of the electrons are in as low an energy level as it is possible
for them to be. When an electron absorbs energy, it occupies a higher energy orbital, and is said
to be in anexcited state.

Properties of Monatomic Ions

The electrons in the outermost shell (the ones with the highest value of n) are the most energetic,
and are the ones which are exposed to other atoms. This shell is known as the valence shell. The
inner, coreelectrons (inner shell) do not usually play a role in chemical bonding.
Elements with similar properties generally have similar outer shell configurations. For instance,
we already know that the alkali metals (Group I) always form ions with a +1 charge; the
"extra" s1 electron is the one that's lost:
IA

Li
Na
K

1s22s1
1s22s22p63s1
1s22s22p63s23p64s1

Li+
Na+
K+

1s2
1s22s22p6
1s22s22p63s23p6

The next shell down is now the outermost shell, which is now full meaning there is very little
tendency to gain or lose more electrons. The ion's electron configuration is the same as the
nearest noble gas the ion is said to be isoelectronic with the nearest noble gas. Atoms "prefer"
to have a filled outermost shell because this is more electronically stable.

The Group IIA and IIIA metals also tend to lose all of their valence electrons to form
cations.
Be 1s22s2
Mg 1s22s22p63s2
IIIA Al 1s22s22p63s23p1
IIA

Be2+
Mg2+
Al3+

1s2
1s22s22p6
1s22s22p6

The Group IV and V metals can lose either the electrons from the p subshell, or from both
the s and p subshells, thus attaining a pseudo-noble gas configuration.
IVA

VA

Sn

[Kr]4d105s25p2

Pb

[Xe]4f145d106s26p2

Bi

[Xe]4f145d106s26p3

Sn2+
Sn4+
Pb2+
Pb4+
Bi3+
Bi5+

[Kr]4d105s2
[Kr]4d10
[Xe]4f145d106s2
[Xe]4f145d10
[Xe]4f145d106s2
[Xe]4f145d10

The Group IV - VII non-metals gain electrons until their valence shells are full (8
electrons).
IVA
VA
VIA
VIIA

1s22s22p2
1s22s22p3
1s22s22p4
1s22s22p5

C4N3O2F-

1s22s22p6
1s22s22p6
1s22s22p6
1s22s22p6

The Group VIII noble gases already possess a full outer shell, so they have no tendency
to form ions.
VIIIA

C
N
O
F

Ne
Ar

1s22s22p6
1s22s22p63s23p6

Transition metals (B-group) usually form +2 charges from losing the valence s electrons,
but can also lose electrons from the highest d level to form other charges.

B-group

Fe

1s22s22p63s23p63d64s2

Fe2+
Fe3+

1s22s22p63s23p63d6
1s22s22p63s23p63d5

The Bohr model was a one-dimensional model that used one quantum number to
describe the distribution of electrons in the atom. The only information that was
important was the size of the orbit, which was described by the n quantum number.
Schrdinger's model allowed the electron to occupy three-dimensional space. It
therefore required three coordinates, or three quantum numbers, to describe the
orbitals in which electrons can be found.
The three coordinates that come from Schrdinger's wave equations are the principal
(n), angular (l), and magnetic (m) quantum numbers. These quantum numbers
describe the size, shape, and orientation in space of the orbitals on an atom.
The principal quantum number (n) describes the size of the orbital. Orbitals for
which n = 2 are larger than those for which n = 1, for example. Because they have
opposite electrical charges, electrons are attracted to the nucleus of the atom. Energy
must therefore be absorbed to excite an electron from an orbital in which the electron
is close to the nucleus (n = 1) into an orbital in which it is further from the nucleus

(n = 2). The principal quantum number therefore indirectly describes the energy of an
orbital.
The angular quantum number (l) describes the shape of the orbital. Orbitals have
shapes that are best described as spherical (l = 0), polar (l = 1), or cloverleaf (l = 2).
They can even take on more complex shapes as the value of the angular quantum
number becomes larger.
There is only one way in which a sphere (l = 0) can be oriented in space. Orbitals that
have polar (l = 1) or cloverleaf (l = 2) shapes, however, can point in different
directions. We therefore need a third quantum number, known as the magnetic
quantum number (m), to describe the orientation in space of a particular orbital. (It is
called the magnetic quantum number because the effect of different orientations of
orbitals was first observed in the presence of a magnetic field.)

Rules Governing the Allowed Combinations of Quantum Numbers

The three quantum numbers (n, l, and m) that describe an orbital are integers: 0,
1, 2, 3, and so on.
The principal quantum number (n) cannot be zero. The allowed values of n are
therefore 1, 2, 3, 4, and so on.
The angular quantum number (l) can be any integer between 0 and n - 1. If n =
3, for example, l can be either 0, 1, or 2.
The magnetic quantum number (m) can be any integer between -l and +l. If l =
2, m can be either -2, -1, 0, +1, or +2.

Shells and Subshells of Orbitals

Orbitals that have the same value of the principal quantum number form a shell.
Orbitals within a shell are divided into subshells that have the same value of the
angular quantum number. Chemists describe the shell and subshell in which an orbital
belongs with a two-character code such as 2p or 4f. The first character indicates the
shell (n = 2 or n = 4). The second character identifies the subshell. By convention, the
following lowercase letters are used to indicate different subshells.

s:
p:
d:
f:

l=0
l=1
l=2
l=3

Although there is no pattern in the first four letters (s, p, d, f), the letters progress
alphabetically from that point (g, h, and so on). Some of the allowed combinations of
the n and l quantum numbers are shown in the figure below.

The third rule limiting allowed combinations of the n, l, and m quantum numbers has
an important consequence. It forces the number of subshells in a shell to be equal to
the principal quantum number for the shell. The n = 3 shell, for example, contains
three subshells: the 3s, 3p, and 3d orbitals.

Possible Combinations of Quantum Numbers

There is only one orbital in the n = 1 shell because there is only one way in which a
sphere can be oriented in space. The only allowed combination of quantum numbers
for which n = 1 is the following.
n

1s

There are four orbitals in the n = 2 shell.

n
2
2
2

l
0
1
1

m
0
-1
0

2s
2p

There is only one orbital in the 2s subshell. But, there are three orbitals in the
2p subshell because there are three directions in which a p orbital can point. One of
these orbitals is oriented along the X axis, another along the Y axis, and the third along
the Z axis of a coordinate system, as shown in the figure below. These orbitals are
therefore known as the 2px, 2py, and 2pz orbitals.

There are nine orbitals in the n = 3 shell.

n

-1

-2

-1

3s

3p

3d

There is one orbital in the 3s subshell and three orbitals in the 3p subshell. The n = 3
shell, however, also includes 3d orbitals.
The five different orientations of orbitals in the 3d subshell are shown in the figure
below. One of these orbitals lies in the XY plane of an XYZ coordinate system and is
called the 3dxy orbital. The 3dxz and 3dyz orbitals have the same shape, but they lie
between the axes of the coordinate system in the XZ and YZ planes. The fourth orbital
in this subshell lies along the X and Y axes and is called the 3dx2-y2 orbital. Most of the
space occupied by the fifth orbital lies along the Z axis and this orbital is called the
3dz2 orbital.
The number of orbitals in a shell is the square of the principal quantum number: 1 2 =
1, 22 = 4, 32 = 9. There is one orbital in an s subshell (l = 0), three orbitals in
a p subshell (l = 1), and five orbitals in a dsubshell (l = 2). The number of orbitals in a
subshell is therefore 2(l) + 1.
Before we can use these orbitals we need to know the number of electrons that can
occupy an orbital and how they can be distinguished from one another. Experimental
evidence suggests that an orbital can hold no more than two electrons.

To distinguish between the two electrons in an orbital, we need a fourth quantum

number. This is called the spin quantum number (s) because electrons behave as if
they were spinning in either a clockwise or counterclockwise fashion. One of the
electrons in an orbital is arbitrarily assigned an s quantum number of +1/2, the other is
assigned an s quantum number of -1/2. Thus, it takes three quantum numbers to define
an orbital but four quantum numbers to identify one of the electrons that can occupy
the orbital.
The allowed combinations of n, l, and m quantum numbers for the first four shells are
given in the table below. For each of these orbitals, there are two allowed values of the
spin quantum number, s.

Summary of Allowed Combinations of Quantum Numbers

Number of
Number of
Total Number of
Subshell Orbitals in the Electrons Needed
Electrons in
n l m
Notation
Subshell
to Fill Subshell
Subshell

1 0 0
1s
1
2
2

2 0 0
2s
1
2
2 1 1,0,-1
2p
3
6
8

3 0 0
3s
1
2
3 1 1,0,-1
3p
3
6
2,1,0,3 2
3d
5
10
18
1,-2

4 0 0
4s
1
2
4 1 1,0,-1
4p
3
6
2,1,0,4 2
4d
5
10
1,-2
4 3 3,2,1,0
4f
7
14
32

,-1,-2,3

Quantum Numbers
A total of four quantum numbers were developed to better understand the movement and pathway of electrons in its
designated orbital within an atom. Each quantum number indicates an electron's trait within an atom, which satisfies
to explain the movement of electrons as a wave function, described by the Schrdinger equation. Each electron in an
atom has a unique set of quantum numbers; no two electrons can share the same combination of four quantum
numbers. Quantum numbers are very significant because they can determine the electron configuration of an atom
and a probable location of the atom's electrons. They can also aid in graphing orbitals. Quantum numbers can help
determine other characteristics of atoms, such as ionization energy and the atomic radius.

The Four Quantum Numbers

Quantum numbers designate specific levels, subshells, orbitals, and spins of electrons. This means that they are
describing in detail the characteristics of the electrons in the atoms. They describe each unique solution to
the Schrdinger equation, or the wave function, of electrons in an atom. There are a total of four quantum numbers:
the principal quantum number (n), the orbital angular momentum quantum number (l), the magnetic quantum number
(ml), and the electron spin quantum number (ms). The principal quantum number, n, describes the energy of an
electron and the most probable distance of the electron from the nucleus. In other words, it is referring to the size of
the orbital and the energy level an electron is placed in. The number of subshells, or l, describes the shape of the
orbital. You can also use l to find the number of angular nodes. The magnetic quantum number, ml, describes the
amount of energy levels in a subshell. ms is referring to the spin on the electron, which can either be up or down.

Principal Quantum Number

The principal quantum number, n, designates the principal electron shell. Because n describes the most probable
distance of the electrons from the nucleus, the larger the number n is, the farther the electrons are from the nucleus,
the larger the size of the orbital, and the larger the atom is. n can be any positive integer starting at 1, as n=1
designates the first principal shell (the innermost shell). The first principal shell is also called the ground state, or
lowest energy state. This explains why n can not be 0 or any negative integer, because there exists no atoms with
zero or a negative amount of energy levels/principal shells. When an electron is in an excited state or it gains energy,
it may jump to the second principle shell, where n=2. This is called absorption because the electron is "absorbing"
photons, or energy. Known as emission, electrons can also "emit" energy as they jump to lower principle shells,
where n decreases by whole numbers. As energy of the electron increases, so does the principal quantum number.
n=3 designates the third principal shell, n=4 designates the fourth principal shell, and so on.
n=1,2,3,4

Example
Given that n=7, what principal electron shell does this refer to?
SOLUTION

Example
If an electron shifted from energy level n=5 to energy level n=3, did absorption or emission of a photon occur?
SOLUTION
Emission because energy was lost, or a photon was "emitted."

Orbital Angular Momentum Quantum Number

The orbital angular momentum quantum number l determines the shape of an orbital, and therefore the angular
distribution. The number of angular nodes is equal to the value of the angular momentum quantum number l. (For
more information about angular nodes, see Electronic Orbitals.) Each value of l indicates a specific s, p, d, f subshell
(each unique in shape.) The value of l is dependent on the principal quantum number n. Unlike n, the value of l can
be zero. It can also be a positive integer, but it cannot be larger than one less than the principal quantum number (n1):
l=0, 1, 2, 3, 4, (n-1)

Example 1
If n=7, what are the possible values of l?
Answer: Since l can be zero or a positive integer less than (n-1), it can have a value of 0, 1, 2, 3, 4, 5 or 6.

Example 2
If l=4, how many angular nodes does the atom have?
Answer: The number of angular nodes is equal to the value of l, so the number of nodes is also 4.

Magnetic Quantum Number

The magnetic quantum number ml determines the number of orbitals and their orientation within a subshell.
Consequently, its value depends on the orbital angular momentum quantum number l. Given a certain l, ml is an
interval ranging from l to +l, so it can be zero, a negative integer, or a positive integer.

ml= -l, (-l +1),( -l +2),, -2, -1, 0, 1, 2, (l 1), (l 2), +l

Example: If n=3, and l=2, then what are the possible values of ml ?
Answer: Since ml must range from l to +l, then ml can be: -2, -1, 0, 1, or 2.

Electron Spin Quantum Number

Unlike n, l, and ml, the electron spin quantum number ms does not depend on another quantum number. It
designates the direction of the electron spin and may have a spin of +1/2, represented by, or 1/2, represented by .
This means that when ms is positive the electron has an upward spin, which can be referred to as "spin up." When it
is negative, the electron has a downward spin, so it is "spin down." The significance of the electron spin quantum
number is its determination of an atom's ability to generate a magnetic field or not. (For more information,
see Electron Spin.)
ms= +1/2 or -1/2

Example
List the possible combinations of all four quantum numbers when n=2, l=1, and ml=0. ms.
SOLUTION

The fourth quantum number is independent of the first three, allowing the first three quantum numbers of two electrons to be the same. Since the sp
can be +1/2 or =1/2, there are two combinations: n=2, l=1, m l =0, ms=+1/2 and n=2, l=1, ml=0 ms=-1/2

Example
Can an electron with ms=1/2 have a downward spin?
SOLUTION

No, if the value of ms is positive, the electron is "spin up."

A Closer Look at Shells, Subshells, and

Orbitals
Principal Shells
The value of the principal quantum number n is the level of the principal electronic shell (principal level). All orbitals
that have the same n value are in the same principal level. For example, all orbitals on the second principal level
have a principal quantum number of n=2. When the value of n is higher, the number of principal electronic shells is
greater. This causes a greater distance between the farthest electron and the nucleus. As a result, the size of the
atom and its atomic radius increases.

Because the atomic radius increases, the electrons are farther from the nucleus. Thus it is easier for the atom to
expel an electron because the nucleus does not have as strong a pull on it, and the ionization energy decreases.

Example
Which orbital has a higher ionization energy, one with n=3 or n=2?
SOLUTION
The orbital with n=2, because the closer the electron is to the nucleus or the smaller the atomic radius, the more energy it takes to expel an electron.

Subshells
The number of values of the orbital angular number l can also be used to identify the number of subshells in a
principal electron shell:

When n = 1, l= 0 (l takes on one value and thus there can only be one subshell)
When n = 2, l= 0, 1 (l takes on two values and thus there are two possible subshells)
When n = 3, l= 0, 1, 2 (l takes on three values and thus there are three possible subshells)
After looking at the examples above, we see that the value of n is equal to the number of subshells in a principal
electronic shell:

Principal shell with n = 1 has one subshell

Principal shell with n = 2 has two subshells
Principal shell with n = 3 has three subshells
To identify what type of possible subshells n has, these subshells have been assigned letter names. The value of l
determines the name of the subshell:
Name of Subshell

Value of l

s subshell

p subshell

d subshell

f subshell

Therefore:

{C}{C}{C}Principal shell with n = 1 has one s subshell (l = 0)

Principal shell with n = 2 has one s subshell and one p subshell (l = 0, 1)

Principal shell with n = 3 has one s subshell, one p subshell, and one d subshell (l = 0, 1, 2)
We can designate a principal quantum number, n, and a certain subshell by combining the value of n and the name of
the subshell (which can be found using l). For example, 3p refers to the third principal quantum number (n=3) and the
p subshell (l=1).

Example
What is the name of the orbital with quantum numbers n=4 and l=1?
SOLUTION
Knowing that the principal quantum number n is 4 and using the table above, we can conclude that it is 4p.

Example
What is the name of the oribital(s) with quantum number n=3?
SOLUTION
3s, 3p, and 3d. Because n=3, the possible values of l = 0, 1, 2, which indicates the shapes of each subshell.

Orbitals
The number of orbitals in a subshell is equivalent to the number of values the magnetic quantum number ml takes on.
A helpful equation to determine the number of orbitals in a subshell is 2l +1. This equation will not give you the value
of ml, but the number of possible values that ml can take on in a particular orbital. For example, if l=1 and ml can
have values -1, 0, or +1, the value of 2l+1 will be three and there will be three different orbitals. The names of the
orbitals are named after the subshells they are found in:
s
orbitals

p
orbitals

d orbitals

f orbitals

ml

-1, 0, +1

-2, -1, 0, +1, -3, -2, -1, 0, +1, +2,

+2
+3

s
orbitals
Number
subshell

of

orbitals

in

designated 1

p
orbitals

d orbitals

f orbitals

In the figure below, we see examples of two orbitals: the p orbital (blue) and the s orbital (red). The red s orbital is a
1s orbital. To picture a 2s orbital, imagine a layer similar to a cross section of a jawbreaker around the circle. The
layers are depicting the atoms angular nodes. To picture a 3s orbital, imagine another layer around the circle, and so
on and so on. The p orbital is similar to the shape of a dumbbell, with its orientation within a subshell depending on
ml. The shape and orientation of an orbital depends on l and ml.
To visualize and organize the first three quantum numbers, we can think of them as constituents of a house. In the
following image, the roof represents the principal quantum number n, each level represents a subshell l, and each
room represents the different orbitals ml in each subshell. The s orbital, because the value of ml can only be 0, can
only exist in one plane. The p orbital, however, has three possible values of ml and so it has three possible
orientations of the orbitals, shown by Px, Py, and Pz. The pattern continues, with the d orbital containing 5 possible
orbital orientations, and f has 7:

quantum
number are depicted in different areas of this diagram.

Restrictions
principal quantum number. There must be an integral number of wavelengths (n) in order for an electron to maintain a
standing wave. If there were to be partial waves, the whole and partial waves would cancel each other out and the

particle would not move. If the particle was at rest, then its position and momentum would be certain. Because this is
not so, n must have an integral value. It is not that the principal quantum number can only be measured in integral
numbers, it is because the crest of one wave will overlap with the trough of another, and the wave will cancel out.

Problems
1.
2.
3.
4.
5.

1. Suppose that all you know about a certain electron is that its principal quantum number is 3. What are the
possible values for the other four quantum numbers?
2. Is it possible to have an electron with these quantum numbers: n=2, l=1, ml=3, ms=1/2? Why or why not?
3. Is it possible to have two electrons with the same n, l, and ml?
4. How many subshells are in principal quantum level n=3?
5. What type of orbital is designated by quantum numbers n=4, l=3, and ml =0?

Solutions
1. When n=3, l=0, ml = 0, and ms=+1/2 or -1/2
l=1 ml = -1, 0, or +1, and ms=+1/2 or -1/2
l=2 ml = -2, -1, 0, 1, or +2, and ms=+1/2 or -1/2
2. No it is not possible. ml=3 is not in the range of -l to +l. The value should be be either -1, 0, or +1.
3. Yes it is possible to have two electrons with the same n, l, and ml. The spin of one electron must be +1/2 while the
spin of the other electron must be -1/2.
4. There are three subshells in principal quantum level n=3.
5. Since l=3 refers to the f subshell, the type of orbital represented is 4f (combination of the principal quantum number
n and the name of the subshell).