Quantum Numbers for Atoms

A total of four quantum numbers are used to describe completely the movement and
trajectories of each electron within an atom. The combination of all quantum numbers of all
electrons in an atom is described by a wave function that complies with the Schrödinger
equation. Each electron in an atom has a unique set of quantum numbers; according to
the Pauli Exclusion Principle, no two electrons can share the same combination of four
quantum numbers. Quantum numbers are important because they can be used to determine
the electron configuration of an atom and the probable location of the atom's electrons.
Quantum numbers are also used to understand other characteristics of atoms, such as
ionization energy and the atomic radius.

In atoms, 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, nn, describes the
energy of an electron and the most probable distance of the electron from the nucleus. In
other words, it refers to the size of the orbital and the energy level an electron is placed in.
The number of subshells, or ll, describes the shape of the orbital. It can also be used to
determine the number of angular nodes. The magnetic quantum number, ml, describes the
energy levels in a subshell, and ms refers to the spin on the electron, which can either be up
or down.

The Principal Quantum Number (nn)

The principal quantum number, nn, 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 electron is 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=1n=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 nn 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=2n=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 the
energy of the electron increases, so does the principal quantum number, e.g., n = 3
indicates the third principal shell, n = 4 indicates the fourth principal shell, and so on.

n=1,2,3,4…(1)(1)n=1,2,3,4…

Example 11

If n = 7, what is the principal electron shell?

Example 22

If an electron jumped from energy level n = 5 to energy level n = 3, did absorption or

emission of a photon occur?

Answer

The Orbital Angular Momentum Quantum Number (ll)

The orbital angular momentum quantum number ll 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 ll. (For more information about angular nodes,
see Electronic Orbitals.) Each value of ll indicates a specific s, p, d, f subshell (each unique in
shape.) The value of ll is dependent on the principal quantum number nn. Unlike nn, the
value of ll can be zero. It can also be a positive integer, but it cannot be larger than one less
than the principal quantum number (n−1n−1):

l=0,1,2,3,4…,(n−1)(2)(2)l=0,1,2,3,4…,(n−1)

Example 33

If n=7n=7, what are the possible values of ll?

Answer

Example 44

If l=4l=4, how many angular nodes does the atom have?

Answer

The Magnetic Quantum Number (mlml)

The magnetic quantum number mlml determines the number of orbitals and their
orientation within a subshell. Consequently, its value depends on the orbital angular
momentum quantum number ll. Given a certain ll, mlml is an interval ranging from –l–
l to +l+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–2),(l–1),+l(3)(3)ml=−l,(−l+1),(−l+2),…,
−2,−1,0,1,2,…(l–2),(l–1),+l

Example 55

Example: If n=3n=3, and l=2l=2, then what are the possible values of mlml?

Answer

The Electron Spin Quantum Number (msms)

Unlike nn, ll, and mlml, the electron spin quantum number msms 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 msms 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. (Electron Spin.)

ms=±12(4)(4)ms=±12

Example 55

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

Answer
Example 66

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

Answer

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 77

Which orbital has a higher ionization energy, one with n=3n=3 or n=2n=2?

Answer

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 ll

s subshell 0

p subshell 1

d subshell 2

f subshell 3

Therefore:

 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 88

What is the name of the orbital with quantum numbers n=4 and l=1?

Answer

Example 99

What is the name of the oribital(s) with quantum number n=3?

Answer

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 p d f orbitals
orbital orbital orbitals
s s

l 0 1 2 3

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

+1 +1, +2 +1, +2, +3

Number of orbitals in 1 3 5 7
designated subshell

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 m l.

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:
Another helpful visual in looking at the possible orbitals and subshells with a set of quantum
numbers would be the electron orbital diagram. (For more electron orbital diagrams,
see Electron Configurations.) The characteristics of each quantum number are depicted in
different areas of this diagram.
Restrictions

 Pauli Exclusion Principle: In 1926, Wolfgang Pauli discovered that a set of quantum
numbers is specific to a certain electron. That is, no two electrons can have the same
values for n, l, ml, and ms. Although the first three quantum numbers identify a
specific orbital and may have the same values, the fourth is significant and must
have opposite spins.

 Hund's Rule: Orbitals may have identical energy levels when they are of the same
principal shell. These orbitals are called degenerate, or "equal energy." According to
Hund's Rule, electrons fill orbitals one at a time. This means that when drawing
electron configurations using the model with the arrows, you must fill each shell with
one electron each before starting to pair them up. Remember that the charge of an
electron is negative and electrons repel each other. Electrons will try to create
distance between it and other electrons by staying unpaired. This further explains
why the spins of electrons in an orbital are opposite (i.e. +1/2 and -1/2).

 Heisenberg Uncertainty Principle: According to the Heisenberg Uncertainty Principle,

we cannot precisely measure the momentum and position of an electron at the same
time. As the momentum of the electron is more and more certain, the position of the
electron becomes less certain, and vice versa. This helps explain integral quantum
numbers and why n=2.5 cannot exist as a 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.
References

1. Chang, Raymond. Physical Chemistry for the Biosciences. 2005, University Science
Books. pp 427-428.

2. Gillespie, Ronald. Demystifying Introductory Chemistry. The Forum: A Contribution

from the Task Force on General Chemistry. 1996: 73;617-622.

3. Petrucci, Ralph. General Chemistry: Principles and Modern Applications, Tenth Edition.

Problems

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=2n=2, l=1l=1, ml=3ml=3, ms=1/2ms=1/2? Why or why not?

3. Is it possible to have two electrons with the same nn, ll, and mlml?

4. How many subshells are in principal quantum level n=3n=3?

5. What type of orbital is designated by quantum numbers n=4n=4, l=3l=3,

and ml=0ml=0?