Electronic Configuration of Elements
Mendeleev noticed the recurrence of properties of elements as the atomic weight increased, and he invented the Periodic table of the element, which is a useful tool for organizing and correlating chemical and physical properties of chemical elements. Today, the most popular Periodic Table form is shaped by results of quantum theory.
Quantum theory rationalized the existence of and arrangement of all elements in today's Periodic Table. It has also been applied to explain their chemical properties.
Electronic Configuration of Elements
Skills to develop
- Explain the rules for filling electrons in atomic orbitals -- Pauli exclusion principle and Hund's rule
- Fill electrons in atomic orbitals--Aufbau process
- Explain the arrangement of elements in terms of quantum numbers
- Explain the systematic variation of element properties
Energy Levels in Many-Electron Atoms
In order to fill the electrons in various atomic orbitals, we need to know how the energy levels vary as the nuclear charge increases. For hydrogen-like atoms, the approximate energy levels are as indicated below:
| Energy levels of H-like atoms :::::: : ::: ::::: ::::::: 4s4p4d4f - --- ----- ------- 3s3p3d - --- -----
2s2p - ---
(a large gap)
1s -
|
The shielding effect and electron-electron interactions cause the energy levels of subshells such as 2s & 2p to be different from those of H-like atoms. This is done by treating the electron shield cores as a proton but the core has an effective nuclear charge Z.

For the H-like atoms, energy levels for 2
s, 2
p stay the same, but the separation between 2
s and 2
p energy levels increases as the atomic number (
Z) increases. Similar situations happen for 3
s, 3
p, and 3
d energy levels. The energy diagrams of H, Li & K are used to illustrate this point. The color diagram is from a Hyperion website discussing quantum nos. and
structure of atoms.........
| Variation of energy levels for atomic orbitals of some elements |
|---|
H _2s_ _ _2p
_ 1s | Li
_ _ _ 2p _ 2s
_ 1s | Be
_ _ _ 2p
_ 2s
_ 1s | B
_ _ _ 2p
_ 2s
_ 1s | C
_ _ _ 2p
_ 2s
_ 1s | N
_ _ _ 2p
_ 2s
_ 1s | O
_ _ _ 2p
_ 2s
_ 1s | F
_ _ _ 2p
_ 2s
_ 1s |
Understand how the energy level vary is the key to the Aufbau process, because Electrons tend to occupy the lowest energy level available. But before we talk about the Aufbau process, we need to be aware of the Pauli exclusion principle and the Hund's rule.
The Pauli Exclusion Principle
The Pauli exclusion principle suggests that only two electrons with opposite spin can occupy an atomic orbital. Stated another way, no two electrons have the same 4 quantum numbers n, l, m, s. Pauli's exclusion principle can be stated in some other ways, but the idea is that energy states have limit room to accommodate electrons. A state accepts two electrons of different spins.
Hund's rule suggests that electrons prefer parallel spins in separate orbitals of subshells. This rule guides us in assigning electrons to different states in each sub-shell of the atmic orbitals. In other words, electrons fill each and all orbitals in the subshell before they pair up with opposite spins. The aufbau procedure (filling order of atomic orbitals) is used to work out the electron confiturations of all atoms. However, modification should be made by applying Hund's rule to be discussed in the next section.
7p _ _ _
7s _ 5f - - - - - - - 6d ~ ~ ~ ~ ~
6p _ _ _
6s _ 4f - - - - - - - 5d ~ ~ ~ ~ ~
5s _ 4d - - - - - 5p ~ ~ ~
4s _ 3d - - - - - 4p ~ ~ ~
3s _ 3p - - -
2s _ 2p - - -
1s _
Z= 2 10 18 36 54 86
1s2 2s22p6 3s23p6 4s23d104p6 5s24d105p6 6s24f145d106p6
He Ne Ar Kr Xe Rn
Block of elements by last filled atomic orbitals |
|---|
1s 2s 3s 4s 5s 6s 7s | 4f - - - - - 4f 5f - - - - - 5f | 3d - - - 3d 4d - - - 4d 5d - - - 5d 6d - - - 6d | 2p - 2p 3p - 3p 4p - 4p 5p - 5p 6p - 6p 7p - 7p |
The highest atomic orbitals occupied by electrons determine the properties of the elements. According to this scheme, the periodic table can be divided into s, p, d, and f blocks as seen in the table on the right. 1s
2s 2p
3s 3p
4s 3d 4p
5s 4d 5p
6s 4f 5d 6p
7s 5f 6d 7p
When two electrons occupy the same orbital, they not only have different spins (Pauli exclusion principle), the pairing raises the energy slightly. On the other hand, a half filled subshell and a full filled subshell lower the energy, gaining some stability. Bearing this in mind, you will be able to understand why we have the following special electronic configurations. | Cr [Ar]4s1 3d5 | <=All s and d subshells are half full |
| Cu [Ar]4s1 3d10 | <=Prefers a filled d subshell, leaving s with 1 |
| Nb [Kr]5s1 4d4 | <=5s and 4d energy levels are close |
| Mo [Kr]5s1 4d5 | similar to Cr above |
| Tc [Kr]5s2 4d5 | (not special, but think of Hund's rule) |
| Ru [Kr]5s1 4d7 | <= Only 1 5s electron |
| Rh [Kr]5s1 4d8 | <= in both |
| Pd [Kr]5s0 4d10 | <= Note filled 4d and empty 5s |
| Ag [Kr]5s1 4d10 | <= partial filled 5s, but filled d |