CHE 126

Electronic Configuration

Periodicity and building up of the

periodic table

Extraction of metals
Hybridization and shapes of simple
molecules
Comparative chemistry of group IA, IIA
and IVA elements.
•How are the electrons in a given atom
distributed among the various orbitals?
Do they all pile up into just a few
orbitals or do they distribute themselves
more widely?
•How does the expected distribution of
electrons among available orbitals differ
for atoms of different elements?
•To answer these fundamental questions
we need to consider three important rules
or principles governing electronic
configurations.
•The electronic configuration of an atom
is a designation of the distribution of its
electrons among the different electronic
shells and orbitals.
1. Electrons occupy orbitals in such a
way as to minimize the energy of the
atom. The below figure A implies an
order in which electrons occupy orbitals,
first the 1s, then 2s, 2p and so on.
Figure A: The order of filling of
electronic subshells.
Actually, the energy of an atom is not
minimized in most cases just by filling
the principal electronic shells in
succession. At higher quantum numbers
and for certain elements an overlapping
of sublevels occurs, for example, with 4s

filing before 3d in potassium and calcium.

As a result we must establish the order of

filling of orbitals by experiment.

The order obtained is roughly the one
listed below 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p,
5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p
Another useful rule is that for any given
pair of orbitals the one with the lower
total number of n and l quantum numbers
fills first. For example, the 3s orbital
(3+0=3) fills before the 3p (3+1=4).
If the n+l totals are the same for two
orbitals, the one with the lower n value
generally fills first. Thus, the 3d orbital
(3+2=5) fills before the 4p (4+1=5).
2. No two electrons in an atom may have
all four quantum numbers alike- the Pauli
Exclusion Principle. In 1926 Wolfgang
Pauli noted that some lines that should
have been present in emission spectra
were not there. He was able to explain
the absence of these lines by stating that
no two electrons in an atom can have all
four quantum numbers alike.
The first three quantum numbers n, l &
ml determine a specific orbital. Two
electrons may have these three quantum
numbers alike,
but if they do they must have different
values of ms, the spin quantum number.
Another way to state this result is that
only two electrons may exist in the same
orbital and these electrons must have
opposite spins.
Because of this limit of two electrons per
orbital, the capacity of a subshell for
electrons can be obtained by doubling the
number of orbitals in the subshell.
Thus, the s subshell consists of one
orbital having a capacity of two electrons;
the p subshell consists of three orbitals
having a total capacity of 6 electrons and
so on.
The capacity of a principal shell is also

twice the number of orbitals it contains

leading to the expression

maximum number of electrons in the

electronic shell with principal quantum

number n=2n 2
3. The principle of maximum multiplicity-
Hund's rule. When orbitals of identical
energy (those in the same subshell) are
available, electrons occupy these singly
rather than in pairs.
As a result, an atom tends to have as

many unpaired electrons as possible.

This behaviour can be rationalized by

saying that electrons,

because they all carry the same electric
charge seek out empty orbitals of similar
energy in preference to pairing up with
electrons in half-filled orbitals.
Electronic configurations of the
elements
To apply the principles, it is handy to use
shorthand designations.
The electronic configuration of an atom
of carbon is represented in two different
ways below

spdf notation: C 1s22s22p2

Orbital diagram: C

In each of these designations a total of

six electrons must be assigned since the
atomic number of carbon is 6.
The spdf notation denotes the total
number(the superscript) of electrons in
each subshell. The orbital diagram breaks
down each subshell into individual
orbitals (drawn as boxes) and
indicates the number of electrons for
each orbital. This is done with arrows.
An arrow pointing upward corresponds
to one type of spin(+1/2) and an arrow
pointing down to the other spin 1
(- / 2).
Electrons in the same orbital with
opposing (opposite) spins are said to
be paired. The electrons in the 1s and
2s orbitals of carbon atom are paired.
Electrons with the same type of spin are said
to have parallel spins, as in the 2p orbitals of
carbon. The electronic configuration
described above for carbon is called the
ground-state electronic configuration.
•The electron configuration of an atom can
be written as the numbers of electrons in
each shell, separated by a comma.