General Chemistry/Shells and Orbitals

Electron shells
Each shell is subdivided into subshells, which are made up of orbitals, each of which has electrons with different
angular momentum. Each orbital in a shell has a characteristic shape, and is named by a letter. They are: s, p, d,
and f. In a one-electron atom (e.g. H, He +, Li+2, etc.) the energy of each orbital within a particular shell is
identical. However, when there are multiple electrons, they interact and split the orbitals into slightly different
energies. Within any particular shell, the energy of the orbitals depend on the angular momentum of orbitals s, p,
d, and f in order of lowest to highest energy. No two orbitals have the same energy level.
This image shows the orbitals (along with hybrid orbitals for bonding and a sample electron configuration,

explained later).

The s orbital
The simplest orbital in the atom is the 1s orbital. It has no radial or angular nodes: the 1s orbital is simply a
sphere of electron density. A node is a point where the electron probability is zero. As with all orbitals the number
of radial nodes increases with the principle quantum number (i.e. the 2s orbital has one radial node, the 3s has
two etc.). Because the angular momentum quantum number is 0, there is only one choice for the magnetic
quantum number - there is only one s orbital per shell. The s orbital can hold two electrons, as long as they have
different spin quantum numbers.

The p orbitals
Starting from the 2nd shell, there is a set of p orbitals. The angular momentum quantum number of the electrons
confined to p orbitals is 1, so each orbital has one angular node. There are 3 choices for the magnetic quantum
number, which indicates 3 differently oriented p orbitals. Finally, each orbital can accommodate two electrons
(with opposite spins), giving the p orbitals a total capacity of 6 electrons.
The p orbitals all have two lobes of electron density pointing along each of the axes. Each one is symmetrical
along its axis. The notation for the p orbitals indicate which axis it points down, i.e. p x points along the x axis, py
on the y axis and pz up and down the z axis. Note that although p z corresponds to the ml = 0 orbital, px and py are
actually mixtures of ml = -1 and ml = 1 orbitals. The p orbitals are degenerate they all have the same energy. P
orbitals are very often involved in bonding.
2px
2py
2pz

The d orbitals
The first set of d orbitals is the 3d set. The angular momentum quantum number is 2, so each orbital has two
angular nodes. There are 5 choices for the magnetic quantum number, which gives rise to 5 different d orbitals.
Each orbital can hold two electrons (with opposite spins), giving the d orbitals a total capacity of 10 electrons.
Note that all the d orbitals have four lobes of electron density, except for the d z2 orbital, which has two opposing
lobes and a doughnut of electron density around the middle. The d orbitals can be further subdivided into two
smaller sets. The dx2-y2 and dz2 all point directly along the x, y, and z axes. They form an eg set. On the other hand,
the lobes of the dxy, dxz and dyz all line up in the quadrants, with no electron density on the axes. These three
orbitals form the t2g set. In most cases, the d orbitals are degenerate, but sometimes they can split, with the eg and
t2g subsets having different energy. Crystal Field Theory predicts and accounts for this. D orbitals are sometimes
involved in bonding, especially in inorganic chemistry.

The f orbitals
The first set of f orbitals is the 4f subshell. There are 7 possible magnetic quantum numbers, so there are 7 f
orbitals. Their shapes are fairly complicated, and they rarely come up when studying chemistry. There are 14 f
electrons because each orbital can hold two electrons (with opposite spins).