Introduction to the Aufbau Principle in Chemistry

Stable atoms have as many electrons as they do protons in the nucleus. The
electrons gather around the nucleus in quantum orbitals following four basic
rules called the Aufbau principle.

 No two electrons in the atom will share the same four quantum
numbers n, l, m, and s.
 Electrons will first occupy orbitals of the lowest energy level.
 Electrons will fill an orbital with the same spin number until the orbital is
filled before it will begin to fill with the opposite spin number.
 Electrons will fill orbitals by the sum of the quantum numbers n and l.
Orbitals with equal values of (n+l) will fill with the lower n values first.

The second and fourth rules are basically the same. The graphic shows the relative energy levels of the
different orbitals. An example of rule four would be the 2p and 3s orbitals. A 2p orbital is n=2 and l=2 and a
3s orbital is n=3 and l=1. (n+l) = 4 in both cases, but the 2p orbital has the lower energy or lower n value and
will get filled before the 3s shell.

Using the Aufbau Principle

Probably the worst way to use the Aufbau principle to figure the fill order of an atom's
orbitals is to try and memorize the order by brute force.

1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d 7p 8s

Fortunately, there is a much simpler method to get this order:

1. Write a column of 's' orbitals from 1 to 8.

2. Write a second column for the 'p' orbitals starting at n=2. (1p is not an orbital
combination allowed by quantum mechanics)
3. Write a column for the 'd' orbitals starting at n=3.
4. Write a final column for 4f and 5f. There are no elements that will need a 6f or 7f
shell to fill.
5. Finally, read the chart by running the diagonals starting from 1s.

The graphic shows this table and the arrows follow the path to follow.

Now that the order of orbitals are known to fill, all that remains is memorizing how large each orbital is.

 s orbitals have 1 possible value of m to hold 2 electrons.

 p orbitals have 3 possible value of m to hold 6 electrons.
 d orbitals have 5 possible value of m to hold 10 electrons.
 f orbitals have 7 possible value of m to hold 14 electrons.

This is all that is needed to determine the electron configuration of a stable atom of an element.

For an example, take the element nitrogen. Nitrogen has seven protons and therefore seven electrons. The
first orbital to fill is the 1s orbital. An s orbital holds two electrons, so five electrons are left. The next orbital is
the 2s orbital and holds the next two. The final three electrons will go to the 2p orbital which can hold up to
six electrons.

Silicon Electron Configuration Example Problem

This is a worked example problem showing the steps necessary to determine

the electron configuration of an element using the principles learned in the
previous sections

Question:

Determine the electron configuration of silicon.

Solution:
Silicon is element 14. It has 14 protons and 14 electrons. The lowest energy level of an atom is filled first. The
arrows in the graphic show the s quantum numbers, spin 'up' and spin 'down'.

Step A shows the first two electrons filling the 1s orbital and leaving 12 electrons.

Step B shows the next two electrons filling the 2s orbital leaving 10 electrons.

The 2p orbital is the next available energy level and can hold six electrons. Step C shows these six electrons
and leaves us with four electrons.

Step D fills the next lowest energy level, 3s with two electrons.

Step E shows the remaining two electrons starting to fill the 3p orbital. Remember one of the rules of the
Aufbau principle is that the orbitals are filled by one type of spin before the opposite spin starts to appear. In
this case, the two spin up electrons are placed in the first two empty slots, but the actual order is arbitrary. It
could have been the second and third slot or the first and third.

Answer

The electron configuration of silicon is 1s22s2p63s23p2.

Notation and Exceptions to the Aufbau Principal

The notation seen on period tables for electron configurations

uses the form:

nOe

n is the energy level

O is the orbital type (s, p, d, or f)
e is the number of electrons in that orbital shell.

For example, oxygen has 8 protons and 8 electrons. The

Aufbau principle has the first two electrons would fill the 1s orbital. The next two would fill the 2s orbital
leaving the remaining four electrons to take spots in the 2p orbital. This would be written as

1s22s2p4

The noble gases are the elements that fill their largest orbital completely with no leftover electrons. Neon fills
the 2p orbital with its last six electrons and would be written as

1s22s2p6

The next element, sodium would be the same with one additional electron in the 3s orbital. Rather than
writing

1s22s2p43s1

and taking up a long row of repeating text, a shorthand notation is used

[Ne]3s1

Each period will use the notation of the previous period's noble gas.

The Aufbau principle works for nearly every element tested. There are two exceptions to this
principle, chromium, and copper.

Chromium is element 24 and according to the Aufbau principle, the electron configuration should be
[Ar]3d4s2. Actual experimental data shows the value to be [Ar]3d5s1.

Copper is element 29 and should be [Ar]3d92s2, but it has been to be determined to be [Ar]3d104s1.

The graphic shows the trends of the periodic table and the highest energy orbital of that element. It is a great
way to check your calculations. Another method of checking is to use a periodic table that has this information
on it already.
Definition of the Pauli Exclusion Principle
Chemistry Definition of Pauli's Exclusion Principle
The Pauli exclusion principle says that every electron must be in its own unique state. In other words, no
electrons in an atom are permitted to have an identical set of quantum numbers.

The Pauli exclusion principle sits at the heart of chemistry, helping

to explain the electron arrangements in atoms and molecules, and
helping to rationalize patterns in the periodic table.

In chemistry the Pauli exclusion principle is applied solely to

electrons, which we are about to discuss.

Wolfgang Pauli received the 1945 Nobel Prize in Physics for

his discovery as it applied to electrons.

Later the Pauli exclusion principle was found to have a

broader meaning, which we will mention at the end of this
page.

Four Quantum Numbers

Every electron in an atom can be defined completely by four quantum numbers:

• n: the principal quantum number

• l: the orbital angular momentum quantum number

• ml: the magnetic quantum number

• ms: the spin quantum number

Example of the Pauli Exclusion Principle

Consider argon's electron configuration:

1s2 2s2 2p6 3s2 3p6

The exclusion principle asserts that every electron in an argon atom is in a
unique state.

The 1s level can accommodate two electrons with identical n, l, and ml quantum
numbers. Argon's pair of electrons in the 1s orbital satisfy the exclusion principle
because they have opposite spins, meaning they have different spin quantum
numbers, ms. One spin is +½, the other is -½. (Instead of saying +½ or -½ often

the electrons are said to be spin-up or spin-down .)

The 2s level electrons have a different principal quantum number to those in the 1s orbital. The pair of 2s
electrons differ from each other because they have opposite spins.

The 2p level electrons have a different orbital angular momentum number from those in the s orbitals, hence
the letter p rather than s. There are three p orbitals of equal energy, the p x, py and pz. These orbitals are
different from one another because they have different orientations in space. Each of the px, py and pz orbitals
can accommodate a pair of electrons with opposite spins.

The 3s level rises to a higher principal quantum number; this orbital accommodates an electron pair with
opposite spins.
The 3p level's description is similar to that for 2p, but the principal quantum number is higher: 3p lies at a
higher energy than 2p.

General Definition of the Pauli Exclusion Principle

Electrons belong to a broad class of subatomic particles called fermions. Fermions have spin quantum
numbers with half-integer values.

Quarks (up and down) and leptons (electrons, electron neutrinos, muons, muon neutrinos, taus, and tau
neutrinos) are all fermions.

All fermions and particles derived from fermions, such as protons and neutrons, obey Fermi-Dirac statistics;
this includes obeying the Pauli exclusion principle.

The Pauli exclusion principle says that no two identical fermions can simultaneously occupy the same
quantum state.

The Pauli exclusion principle does not apply to bosons: these are particles that obey Bose-Einstein statistics;
they all have integer values of spin. Photons, gluons, gravitons, and the W, Z and Higgs bosons are all
bosons.
Hund's Rules
The Aufbau section discussed how that electrons fill the lowest energy orbitals first, and then move up to higher energy
orbitals only after the lower energy orbitals are full. However, there a problem with this rule. Certainly, 1s orbitals
should be filled before 2s orbitals, because the 1s orbitals have a lower value of n, and thus a lower energy. What about
the three different 2p orbitals? In what order should they be filled? The answer to this question involves Hund's rule.

Hund's rule states that:

1. Every orbital in a sublevel is singly occupied before any orbital is doubly occupied.
2. All of the electrons in singly occupied orbitals have the same spin (to maximize total spin).

When assigning electrons to orbitals, an electron first seeks to fill all the orbitals with similar energy (also referred to as
degenerate orbitals) before pairing with another electron in a half-filled orbital. Atoms at ground states tend to have as
many unpaired electrons as possible. In visualizing this process, consider how electrons exhibit 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 1.11.1: NITROGEN ATOMS

Consider the correct electron configuration of the nitrogen (Z = 7) atom: 1s2 2s2 2p3

The p orbitals are half-filled; there are three electrons and three p orbitals. This is because the three electrons in
the 2p subshell will fill all the empty orbitals first before pairing with electrons in them.

Keep in mind that elemental nitrogen is found in nature typically as dinitrogen, N2, which requires molecular
orbitals instead of atomic orbitals as demonstrated above.

EXAMPLE 1.21.2: OXYGEN ATOMS

Next, consider oxygen (Z = 8) atom, the element after nitrogen in the same period; its electron configuration is: 1s2 2s2 2p4

Oxygen has one more electron than nitrogen; as the orbitals are all half-filled, the new electron must pair up. Keep in mind
that elemental oxygen is found in nature typically as dioxygen, O2O2, which has molecular orbitals instead of atomic
orbitals as demonstrated above.

Hund's Rule Explained

According to the first rule, electrons always enter an empty orbital before they pair up. Electrons are negatively charged
and, as a result, they repel each other. Electrons tend to minimize repulsion by occupying their own orbitals, rather than
sharing an orbital with another electron. Furthermore, quantum-mechanical calculations have shown that the electrons in
singly occupied orbitals are less effectively screened or shielded from the nucleus. Electron shielding is further discussed in
the next section.
For the second rule, unpaired electrons in singly occupied orbitals have the same spins. Technically speaking, the first
electron in a sublevel could be either "spin-up" or "spin-down." Once the spin of the first electron in a sublevel is chosen,
however, the spins of all of the other electrons in that sublevel depend on that first spin. To avoid confusion, scientists
typically draw the first electron, and any other unpaired electron, in an orbital as "spin-up."

EXAMPLE 1.31.3: CARBON AND OXYGEN

Consider the electron configuration for carbon atoms: 1s22s22p2: The two 2s electrons will occupy the same orbital, whereas
the two 2p electrons will be in different orbital (and aligned the same direction) in accordance with Hund's rule.

Consider also the electron configuration of oxygen. Oxygen has 8 electrons. The electron configuration can be written as
1s22s22p4. To draw the orbital diagram, begin with the following observations: the first two electrons will pair up in the 1s
orbital; the next two electrons will pair up in the 2s orbital. That leaves 4 electrons, which must be placed in the 2p orbitals.
According to Hund’s rule, all orbitals will be singly occupied before any is doubly occupied. Therefore, two p orbital get
one electron and one will have two electrons. Hund's rule also stipulates that all of the unpaired electrons must have the
same spin. In keeping with convention, the unpaired electrons are drawn as "spin-up", which gives (Figure 1).

Purpose of Electron Configurations

When atoms come into contact with one another, it is the outermost electrons of these atoms, or valence shell, that will
interact first. An atom is least stable (and therefore most reactive) when its valence shell is not full. The valence electrons
are largely responsible for an element's chemical behavior. Elements that have the same number of valence electrons often
have similar chemical properties.

Electron configurations can also predict stability. An atom is most stable (and therefore unreactive) when all its orbitals
are full. The most stable configurations are the ones that have full energy levels. These configurations occur in the noble
gases. The noble gases are very stable elements that do not react easily with any other elements. Electron configurations
can assist in making predictions about the ways in which certain elements will react, and the chemical compounds or
molecules that different elements will form.