ATOMIC STRUCTURE: THE QUANTUM MECHANICAL MODEL

Two models of atomic structure are in use today: the Bohr model and the quantum mechanical model. The

quantum mechanical model is based on mathematics. Although it is more difficult to understand than the
Bohr model, it can be used to explain observations made on complex atoms.

The quantum mechanical model is based on quantum theory, which says matter also has properties

associated with waves. According to quantum theory, it’s impossible to know the exact position and
momentum of an electron at the same time. This is known as the Uncertainty Principle.

The quantum mechanical model of the atom uses complex shapes of orbitals(sometimes called electron

clouds), volumes of space in which there is likely to be an electron. So, this model is based on probability

rather than certainty.

Four numbers, called quantum numbers, were introduced to describe the characteristics of electrons and

their orbitals:

 Principal quantum number: n

 Angular momentum quantum number: l

 Magnetic quantum number:

 Spin quantum number:

THE PRINCIPAL QUANTUM NUMBER

The principal quantum number n describes the average distance of the orbital from the nucleus — and the
energy of the electron in an atom. It can have positive integer (whole number) values: 1, 2, 3, 4, and so on.

The larger the value of n, the higher the energy and the larger the orbital. Chemists sometimes call the
orbitals electron shells.

THE ANGULAR MOMENTUM QUANTUM NUMBER

The angular momentum quantum number l describes the shape of the orbital, and the shape is limited by

the principal quantum number n: The angular momentum quantum number l can have positive integer
values from 0 to n–1. For example, if the n value is 3, three values are allowed for l: 0, 1, and 2.
The value of l defines the shape of the orbital, and the value of n defines the size.

Orbitals that have the same value of n but different values of l are called subshells. These subshells are given different

letters to help chemists distinguish them from each other. The following table shows the letters corresponding to the
different values of l.

Letter Designations of the Subshells

Value of l (subshell) Letter

0 s

1 p

2 d

3 f

4 g

When chemists describe one particular subshell in an atom, they can use both the n value and the subshell letter — 2p,

3d, and so on. Normally, a subshell value of 4 is the largest needed to describe a particular subshell. If chemists ever
need a larger value, they can create subshell numbers and letters.

The following figure shows the shapes of the s, p, and d orbitals.

As shown in the top row of the figure (a), there are two s orbitals — one for

energy level 1 (1s) and the other for energy level 2 (2s). The s orbitals are

spherical with the nucleus at the center. Notice that the 2s orbital is larger in

diameter than the 1s orbital. In large atoms, the 1s orbital is nestled inside
the 2s, just like the 2p is nestled inside the 3p.

The second row of the figure (b) shows the shapes of the p orbitals, and the
last two rows (c) show the shapes of the d orbitals. Notice that the shapes get progressively more complex.

THE MAGNETIC QUANTUM NUMBER

The magnetic quantum number is designated as:

This number describes how the various orbitals are oriented in space. The value of this number depends on the value

of l. The values allowed are integers from –lto 0 to +l. For example, if the value of l = 1 (p orbital), you can write three

values for this number: –1, 0, and +1. This means that there are three different p subshells for a particular orbital. The
subshells have the same energy but different orientations in space.

The second row (b) of the figure shows how the p orbitals are oriented in space. Notice that the three p orbitals
correspond to magnetic quantum number values of –1, 0, and +1, oriented along the x, y, and z axes.

THE SPIN QUANTUM NUMBER

The fourth and final quantum number is the spin quantum number, designated as:

This number describes the direction the electron is spinning in a magnetic field — either clockwise or

counterclockwise. Only two values are allowed: +1/2 or –1/2. For each subshell, there can be only two electrons, one
with a spin of +1/2 and another with a spin of –1/2.

 In the Bohr Model, the electron is treated as a particle in fixed orbits around the nucleus. In the
Quantum Mechanical Model, the electron is treated mathematically as a wave. The electron has
properties of both particles and waves.
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 “n” the principle quantum number.
Schrodinger's model (Quantum Mechanical Model) allowed the electron to occupy three-dimensional space.
It therefore required three coordinates, or three quantum numbers, to describe the distribution of electrons
in the atom.

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 determine other characteristics of atoms, such as ionization energy and the atomic
radius.

The Four Electronic Quantum Numbers

Quantum numbers designate specific shells, subshells, orbitals, and spins of electrons. This means that they
describe completely the characteristics of an electron in an atom, i.e., they describe each unique solution to
the Schrödinger 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, 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?

SOLUTION

EXAMPLE 22

If an electron jumped from energy level n = 5 to energy level n = 3, did absorption or emission of a photon
occur?

SOLUTION

Emission, because energy is lost by release of a photon.

The Orbital Angular Momentum Quantum Number (ll)

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 ll. (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 (n-1):

l=0,1,2,3,4…,(n−1)(2)(2)l=0,1,2,3,4…,(n−1)
EXAMPLE 33

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 44

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.
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–1),(l–2),+l(3)(3)ml=−l,(−l+1),(−l+2),…,−2,−1,0,1,2,…(l–1),(l–2),+l
EXAMPLE 55

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

SOLUTION

Answer: Since ml must range from –l to +l, then ml can be: -2, -1, 0, 1, or 2.

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=2, l=1, and ml=0ml=0.

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 spin can be +1/2 or =1/2, there are two combinations: n=2, l=1, ml =0,
ms=+1/2 and n=2, l=1, ml=0 ms=-1/2

EXAMPLE 66

Can an electron with ms=1/2ms=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 77

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

Name of Value
Subshell of ll

s subshell 0

p subshell 1

d subshell 2
To identify what type of possible subshells n has, these subshells have
been assigned letter names. The f subshell 3 value of l determines the name of the
subshell:

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?

SOLUTION

Knowing that the principal quantum number n is 4 and using the table above, we can conclude that it is 4p.

EXAMPLE 99

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 p d f
orbitals orbitals orbitals orbitals

l 0 1 2 3

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

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

Number of 1 3 5 7
orbitals in
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 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:

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.

The electron configuration of an atom is the representation of the arrangement of electrons distributed among
the orbital shells and subshells. Commonly, the electron configuration is used to describe the orbitals of an
atom in its ground state, but it can also be used to represent an atom that has ionized into a cation or anion
by compensating with the loss of or gain of electrons in their subsequent orbitals. Many of the physical and
chemical properties of elements can be correlated to their unique electron configurations. The valence
electrons, electrons in the outermost shell, are the determining factor for the unique chemistry of the element.

Introduction

Before assigning the electrons of an atom into orbitals, one must become familiar with the basic concepts of
electron configurations. Every element on the Periodic Table consists of atoms, which are composed of
protons, neutrons, and electrons. Electrons exhibit a negative charge and are found around the nucleus of
the atom in electron orbitals, defined as the volume of space in which the electron can be found within 95%
probability. The four different types of orbitals (s,p,d, and f) have different shapes, and one orbital can hold a
maximum of two electrons. The p, d, and f orbitals have different sublevels, thus can hold more electrons.
As stated, the electron configuration of each element is unique to its position on the periodic table. The energy
level is determined by the period and the number of electrons is given by the atomic number of the element.
Orbitals on different energy levels are similar to each other, but they occupy different areas in space. The 1s
orbital and 2s orbital both have the characteristics of an s orbital (radial nodes, spherical volume probabilities,
can only hold two electrons, etc.) but, as they are found in different energy levels, they occupy different spaces
around the nucleus. Each orbital can be represented by specific blocks on the periodic table. The s-block is
the region of the alkali metals including helium (Groups 1 & 2), the d-block are the transition metals (Groups
3 to 12), the p-block are the main group elements from Groups 13 to 18, and the f-block are
the lanthanides and actinides series.

Using the periodic table to determine the electron configurations of atoms is key, but also keep in mind that
there are certain rules to follow when assigning electrons to different orbitals. The periodic table is an
incredibly helpful tool in writing electron configurations. For more information on how electron configurations
and the periodic table are linked, visit the Connecting Electrons to the Periodic Table module.

Rules for Assigning Electron Orbitals

Occupation of Orbitals

Electrons fill orbitals in a way to minimize the energy of the atom. Therefore, the electrons in an atom fill the
principal energy levels in order of increasing energy (the electrons are getting farther from the nucleus). The
order of levels filled looks like this:

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, and 7p

One way to remember this pattern, probably the easiest, is to refer to the periodic table and remember where
each orbital block falls to logically deduce this pattern. Another way is to make a table like the one below and
use vertical lines to determine which subshells correspond with each other.
Pauli Exclusion Principle

The Pauli exclusion principle states that no two electrons can have the same four quantum numbers. The first
three (n, l, and ml) may be the same, but the fourth quantum number must be different. A single orbital can
hold a maximum of two electrons, which must have opposing spins; otherwise they would have the same
four quantum numbers, which is forbidden. One electron is spin up (ms = +1/2) and the other would spin down
(ms = -1/2). This tells us that each subshell has double the electrons per orbital. The s subshell has 1 orbital
that can hold up to 2 electrons, the p subshell has 3 orbitals that can hold up to 6 electrons, the d subshell
has 5 orbitals that hold up to 10 electrons, and the f subshell has 7 orbitals with 14 electrons.

EXAMPLE 1: HYDROGEN AND HELIUM

The first three quantum numbers of an electron are n=1, l=0, m l=0. Only two electrons can correspond to
these, which would be either ms = -1/2 or ms = +1/2. As we already know from our studies of quantum numbers
and electron orbitals, we can conclude that these four quantum numbers refer to the 1s subshell. If only one
of the ms values are given then we would have 1s1 (denoting hydrogen) if both are given we would have
1s2 (denoting helium). Visually, this is be represented as:

As shown, the 1s subshell can hold only two electrons and, when filled, the electrons have opposite spins.

Hund's Rule

When assigning electrons in orbitals, each electron will first fill all the orbitals with similar energy (also referred
to as degenerate) before pairing with another electron in a half-filled orbital. Atoms at ground states tend to
have as many unpaired electrons as possible. When visualizing this processes, think about how electrons are
exhibiting the same behavior as the same poles on a magnet would if they came into contact; as the negatively
charged electrons fill orbitals they first try to get as far as possible from each other before having to pair up.

EXAMPLE 2: OXYGEN AND NITROGEN

If we look at the correct electron configuration of the Nitrogen (Z = 7) atom, a very important element in the
biology of plants: 1s2 2s2 2p3
We can clearly see that p orbitals are half-filled as there are three electrons and three p orbitals. This is
because Hund's Rule states that the three electrons in the 2p subshell will fill all the empty orbitals first before
filling orbitals with electrons in them. If we look at the element after Nitrogen in the same period, Oxygen (Z =
8) its electron configuration is: 1s2 2s22p4 (for an atom).

Oxygen has one more electron than Nitrogen and as the orbitals are all half filled the electron must pair up.

The Aufbau Process

Aufbau comes from the German word "aufbauen" meaning "to build." When writing electron
configurations, orbitals are built up from atom to atom. When writing the electron configuration for an
atom, orbitals are filled in order of increasing atomic number. However, there are some exceptions to this rule.

EXAMPLE 3: 3RD ROW ELEMENTS

Following the pattern across a period from B (Z=5) to Ne (Z=10), the number of electrons increases and the
subshells are filled. This example focuses on the p subshell, which fills from boron to neon.

 B (Z=5) configuration: 1s2 2s2 2p1

 C (Z=6) configuration:1s2 2s2 2p2
 N (Z=7) configuration:1s2 2s2 2p3
 O (Z=8) configuration:1s2 2s2 2p4
 F (Z=9) configuration:1s2 2s2 2p5
 Ne (Z=10) configuration:1s2 2s2 2p6
Exceptions

Although the Aufbau rule accurately predicts the electron configuration of most elements, there are notable
exceptions among the transition metals and heavier elements. The reason these exceptions occur is that
some elements are more stable with fewer electrons in some subshells and more electrons in others (Table
1).

Table 1: Exceptions to Electron Configuration Trends

Period 4: Period 5:

Chromium: Z:24 [Ar] 3d54s1 Niobium: Z:41 [Kr] 5s1 4d4

Copper: Z:29 [Ar] 3d104s1 Molybdenum: Z:42 [Kr] 5s14d5

Ruthenium: Z:44 [Kr] 5s1 4d7

Rhodium: Z:45 [Kr] 5s1 4d8

 Palladium: Z:46 [Kr] 4d10

Silver: Z:47 [Kr] 5s1 4d10

Period 6: Period 7:

Lanthanum: Z:57 [Xe] 6s2 5d1 Actinium: Z:89 [Rn] 7s2 6d1

Cerium: Z:58 [Xe] 6s2 4f1 5d1 Thorium: Z:90 [Rn] 7s2 6d2

Gadolinium: Z:64 [Xe] Protactium: Z:91 [Rn]

6s2 4f75d1 7s2 5f26d1

Platinum: Z:78 [Xe] Uranium: Z:92 [Rn] 7s2 5f3 6d1

6s1 4f145d9

Gold: Z:79 [Xe] 6s1 4f14 5d10 Neptunium: Z:93 [Rn]

7s2 5f46d1

Curium: Z:96 [Rn] 7s2 5f7 6d1

Lawrencium: Z:103 [Rn]

7s25f14 7p1

Writing Electron Configurations

When writing an electron configuration, first write the energy level (the period), then the subshell to be filled
and the superscript, which is the number of electrons in that subshell. The total number of electrons is the
atomic number, Z. The rules above allow one to write the electron configurations for all the elements in the
periodic table. Three methods are used to write electron configurations:

1. orbital diagrams
2. spdf notation
3. noble gas notation

Each method has its own purpose and each has its own drawbacks.

Orbital Diagrams

An orbital diagram, like those shown above, is a visual way to reconstruct the electron configuration by
showing each of the separate orbitals and the spins on the electrons. This is done by first determining the
subshell (s,p,d, or f) then drawing in each electron according to the stated rules above.

EXAMPLE 4: ALUMINUM AND IRIDIUM

Write the electron configuration for aluminum and iridium.

SOLUTION

Aluminum is in the 3rd period and it has an atomic number of Z=13. If we look at the periodic table we can
see that its in the p-block as it is in group 13. Now we shall look at the orbitals it will fill: 1s, 2s, 2p, 3s, 3p. We
know that aluminum completely fills the 1s, 2s, 2p, and 3s orbitals because mathematically this would be
2+2+6+2=12. The last electron is in the 3p orbital. Also another way of thinking about it is that as you move
from each orbital block, the subshells become filled as you complete each section of the orbital in the period.
The block that the atom is in (in the case for aluminum: 3p) is where we will count to get the number of
electrons in the last subshell (for aluminum this would be one electron because its the first element in the
period 3 p-block). This gives the following:

Note that in the orbital diagram, the two opposing spins of the electron can be visualized. This is why it is
sometimes useful to think about electron configuration in terms of the diagram. However, because it is the
most time consuming method, it is more common to write or see electron configurations in spdf notation and
noble gas notation. Another example is the electron configuration of iridium:

The electron configuration of iridium is much longer than aluminum. Although drawing out each orbital may
prove to be helpful in determining unpaired electrons, it is very time consuming and often not as practical as
the spdf notation, especially for atoms with much longer configurations. Hund's rule is also followed, as each
electron fills up each 5d orbital before being forced to pair with another electron.

spdf Notation

The most common way to describe electron configurations is to write distributions in the spdf notation.
Although the distributions of electrons in each orbital are not as apparent as in the diagram, the total number
of electrons in each energy level is described by a superscript that follows the relating energy level. To write
the electron configuration of an atom, identify the energy level of interest and write the number of electrons in
the energy level as its superscript as follows: 1s2. This is the electron configuration of helium; it denotes a full
s orbital. The periodic table is used as a reference to accurately write the electron configurations of all atoms.

EXAMPLE 5: YTTRIUM

Write the electronic configuration of Yttrium.

SOLUTION

Start with the straightforward problem of finding the electron configuration of the element yttrium. As
always, refer to the periodic table. The element yttrium (symbolized Y) is a transition metal, found in the fifth
period and in Group 3. In total it has thirty-nine electrons. Its electron configuration is as follows:

1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d1

This is a much simpler and more efficient way to portray electron configuration of an atom. A logical way of
thinking about it is that all that is required is to fill orbitals across a period and through orbital blocks. The
number of elements in each block is the same as in the energy level it corresponds. For example, there are
2 elements in the s-block, and 10 elements in the d-block. Moving across, simply count how many elements
fall in each block. Yttrium is the first element in the fourth period d-block; thus there is one electron in that
energy level. To check the answer, verify that the subscripts add up to the atomic number. In this case,
2+2+6+2+6+2+10+6+2+1= 39 and Z=39, so the answer is correct.

A slightly more complicated example is the electron configuration of bismuth (symbolized Bi, with Z = 83). The
periodic table gives the following electron configuration:

1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p65s2 4d10 5p6 6s2 4f14 5d10 6p3

The reason why this electron configuration seems more complex is that the f-block, the Lanthanide series, is
involved. Most students who first learn electron configurations often have trouble with configurations that must
pass through the f-block because they often overlook this break in the table and skip that energy level. Its
important to remember that when passing the 5d and 6d energy levels that one must pass through the f-
block lanthanoid and actinoid series. Keeping this in mind, this "complex" problem is greatly simplified.

Another method (but less commonly used) of writing the spdf notation is the expanded notation format. This
is the same concept as before, except that each individual orbital is represented with a subscript. The p, d,
and f orbitals have different sublevels. The p orbitals are px, py, and pz, and if represented on the 2p energy
with full orbitals would look like: 2px2 2py2 2pz2. The expanded notation for neon (Ne, Z=10) is written as
follows:

1s2 2s2 2px2 2py2 2pz2

The individual orbitals are represented, but the spins on the electrons are not; opposite spins are assumed.
When representing the configuration of an atom with half filled orbitals, indicate the two half filled orbitals. The
expanded notation for carbon is written as follows:

1s2 2s2 2px1 2py1

Because this form of the spdf notation is not typically used, it is not as important to dwell on this detail as it is
to understand how to use the general spdf notation.

Noble Gas Notation

This brings up an interesting point about elements and electron configurations. As the p subshell is filled in
the above example about the Aufbau principle (the trend from boron to neon), it reaches the group commonly
known as the noble gases. The noble gases have the most stable electron configurations, and are known for
being relatively inert. All noble gases have their subshells filled and can be used them as a shorthand way of
writing electron configurations for subsequent atoms. This method of writing configurations is called the noble
gas notation, in which the noble gas in the period above the element that is being analyzed is used to denote
the subshells that element has filled and after which the valence electrons (electrons filling orbitals in the outer
most shells) are written. This looks slightly different from spdf notation, as the reference noble gas must be
indicated.

EXAMPLE 6: VANADIUM

What is the electronic configuration of vanadium (V, Z=23)?

SOLUTION

Vanadium is the transition metal in the fourth period and the fifth group. The noble gas preceding it is
argon (Ar, Z=18), and knowing that vanadium has filled those orbitals before it, argon is used as the reference
noble gas. The noble gas in the configuration is denoted E, in brackets: [E]. To find the valance electrons that
follow, subtract the atomic numbers: 23 - 18 = 5. Instead of 23 electrons to distribute in orbitals, there are 5.
Now there is enough information to write the electron configuration:

Vanadium, V: [Ar] 4s2 3d3

This method streamlines the process of distributing electrons by showing the valence electrons, which
determine the chemical properties of atoms. In addition, when determining the number of unpaired electrons
in an atom, this method allows quick visualization of the configurations of the valance electrons. In the
example above, there are a full s orbital and three half filled d orbitals.

The main goal of this module is to be able to write the electron configurations for atoms and ions. This web
page will provide an outline of how to write these configurations.

First, a couple of definitions:

 paired spins = two electrons who have opposite spins, one up (or +1/2) and one down (or -
1/2). Frequently the two electrons will be in the same orbital.
 parallel spins = two electrons who have the same spin, both up or both down

Electron Configurations

An electron configuration shows how the electrons are divided up among the orbitals in an atom. There are
three common notations that you should be comfortable with - box, spectroscopic and noble gas.

To begin with, you need to know how many electrons you will be working with in a particular atom or
ion. To review the number of electrons in an atom or ion, see the page in this module's web site called
Counting Electrons in an Atom or Ion.

The overall guiding principle behind the rules which will follow is that we want to take the atom's or ion's
electrons, and arrange them among the orbitals so that the energy of the entire arrangement is the smallest
possible amount. All of these rules are derived from that principle.

The next several section will outline these rules, and then we will put them all together to write the
configurations in several examples.

The Aufbau Principle

This principle simply states that we can build up an electronic configuration one electron at a time by
putting each electron in the lowest energy orbital available. The energy ordering of the orbitals can be
remembered from this diagram which we first saw in the last module:
After you draw the diagram, connect the orbitals in a diagonal fashion as follows. Start with the
1s subshell and draw a diagonal line through it from the lower right to upper left corner. Then, snake that
line back between the 1s and 2s subshells, parallel to the first. Turn this line around and go through the
2s. Turn around again and come back between 2s and 2p. Turn around and go through 2p and
2s. Continue in this fashion until you have worked your way through the diagram.

If you follow this line through the diagram, it traces out the subshells in this order: 1s 2s 2p 3s 3p 4s 3d 4p
5s 4d 5p 6s 4f 5d 6p ...

This is the order of the subshells from lowest energy to highest. When we arrange electrons among orbitals,
we will start with the lowest energy subshell, the 1s, and add electrons until it is filled. Then, we will move
on to the next subshell, the 2s, until it is filled. We will continue in this manner until we run out of electrons.

The Pauli Exclusion Principle

This principle says that an orbital is filled when it contains 2 electrons. After that, you have to put the
electrons in a different orbital.

Let's look at how this translates into subshells. Each type of subshell contains a different number
of orbitals. And, each orbital can hold at most 2 electrons. The following table shows how many electrons
each type of subshell can hold.

Subshell Type # of Orbitals Maximum # of Electrons

s 1 2
p 3 6
d 5 10
f 7 14

Hund's Rule

Within a subshell, the electrons will occupy the orbitals singly first, and will only pair up when there are no
longer any empty orbitals available in that subshell.

Magnetism

Individual atoms and ions are either paramagnetic or diamagnetic (ferromagnetism is a property of bulk
matter, not just an individual atom or ion). To determine whether an atom is paramagnetic or diamagnetic,
look at the box notation for the electron configuration. If all of the electrons are paired, it is diamagnetic. If
one or more electrons are unpaired, it is paramagnetic.

(Remember that paired spins mean that for every electron with spin up, there is one electron with spin
down.)

Examples:
Write the electronic configuration for the following atoms or ions. Use the box notation, spectroscopic
notation and noble gas notation. Are they paramagnetic or diamagnetic?
1. H
2. He
3. C
4. Ne
5. Cl-

Solutions:
1. H = 1 electron (atomic number from the periodic table = 1)

We will start with the lowest energy subshell, the 1s, which has 1 orbital. The single electron is placed in this
orbital.

Box notation: We can explicitly show each electron in each orbital. Each orbital is shown as a box. Each
electron is shown as an arrow. An arrow point up indicates spin up, and an arrow point down indicates spin
down. Each subshell of orbitals is labeled underneath the grouping of orbitals for that subshell.

Spectroscopic notation: The orbital is named, and the number of electrons inside the orbital is shown as a
superscript.
1s1

Hydrogen atoms are paramagnetic with one unpaired electron.

2. Helium:
The atomic number is 2, so He has 2 electrons to place.

Spectroscopic Notation: He = 1s2

Box notation:

Note that helium is diamagnetic since all of the electrons are paired. Note, also, that the 1s subshell is now
filled since it only contains one orbital and can hold at most 2 electrons.

3. Carbon:
Atomic number = 6, so C has 6 electrons to place.
The 1s subshell is filled with just 2 electrons. From the Aufbau diagram above, we see that the
next subshell to fill is the 2s. It will also be filled with 2 electrons, so we will have to move to the
2p subshell for the remaining 2 electrons.

spectroscopic notation: C = 1s22s22p2

Noble gas core notation: Instead of writing out all of the electrons in the configuration, we can write out
just the ones since the last noble gas. Find carbon on the periodic table, and then go backwards until you
reach a noble gas. In this case, it is helium. We can use a shorthand to indicate all of the electrons that are
identical to helium's configuration by putting He in square brackets, and substituting it for those electrons.

Noble Gas Core Notation: C = [He]2s22p2

In this case, we did not really save any effort, but for much bigger atoms, the noble gas core notation can be
very convenient.

Box notation: Each s subshell has one orbital, but the p subshell has 3 orbitals. Hund's rule tells us that we
have to put the 2p
electrons in separate orbitals since there is room to do so.
Thus, carbon is paramagnetic with two unpaired electrons.

4. Neon:
Atomic number = 10, so there are 10 electrons to place.

Spectroscopic Notation: Ne = 1s22s22p6

Noble gas core notation: [Ne]

Box notation:

Since all of neon's electrons are paired, it is diamagnetic. The six electrons in the p subshell completely fill
it. If you needed to place 11 electrons (for sodium) you would have to go to the next subshell, 3s.

5. Cl-
Atomic number = 17 for Cl; Add 1 for the anion = 18 electrons in Cl-

Spectroscopic Notation: 1s22s22p63s23p6

Noble gas core notation: [Ar]

Box notation: