Electronic configuration

PREPARED BY: A. HARRIS

 2

Atomic Orbitals

 Recall:
 The atomic orbital is the volume of space within an atom where there is a high
probability (approx. 95% chance) of finding the electron.

 There is about a 5% probability that the electron will be outside this volume of
space at any given instant.
 3
Quantum-Mechanical Model

 The quantum mechanical model of the atom treats the atom as having both particulate and wave properties.

 Atoms exist only in certain definite energy states. When an atoms changes its energy state it must absorb or
emit just enough  energy to bring it to its new energy state.

 The change in energy of the atom is related to the frequency or wavelength of the light absorbed or emitted

 The location/energy of electrons in an atom can be described using four quantum numbers.

 They include; principal quantum number (n), sub-shell (l), orbital (ml), orbital spin (ms)

 These quantum numbers act as an address for an electron in an atom

 Quantum numbers

10/6/2015
 Principal quantum number, n
 It describes the energy level of the electron

Shell No of electron Energy level No of electron

1st 2 n=1 2
2nd 8 n=2 8
3rd 18 ( 8 then 10) n=3 18

4th 32 n=4 32 4
 Quantum numbers

10/6/2015
 Angular quantum number, l
 Describes the sublevels/subshells in the principal quantum number as well as the type of orbitals which exist
in each
 Each energy level has sublevels equivalent to its value of n

value of n # of sublevel Name of sublevel (orbital)

1 1 1s

2 2 2s 2p

3 3 3s 3p 3d

4 4 4s 4p 4d 4f 5
 Quantum numbers

10/6/2015
 Magnetic quantum number, m
 Describes the number of orbitals within a sublevel
orbitals # electrons # of orbitals

S 2 One at each level

P 6 Px , Py, Pz ( 3 orbitals)

D 10 d1 d2 d3 d4 d5 (5 orbitals)

F 14 (7 orbitals)

6
 Each orbital can accommodate a maximum of two electrons
 This is tied to the existence of a 4th quantum number, the electron spin quantum number, ms.
 7
Arrangement of Electrons in Atoms

Electrons in atoms are arranged as

SHELLS (n)

SUBSHELLS (l)

ORBITALS (ml)
 8

QUANTUM
QUANTUM
NUMBERS
NUMBERS

nn --->
---> shell
shell 1,
1, 2,
2, 3,
3, 4,
4, ...
...
ll --->
---> subshell
subshell 0,
0, 1,
1, 2,
2, ...
... nn -- 11
m
ml l --->
---> orbital
orbital -l-l ...
... 00 ...
... +l
+l
m
mss --->
---> electron
electron spin
spin +1/2
+1/2 and
and -1/2
-1/2
 9
For our Purposes….

n ---> shell 1, 2, 3, 4, ...

l ---> sub-shell (s, p, d, f …)
ml ---> orbital □
ms ---> electron spin ↑↓
 10
Pauli Exclusion Principle

No two electrons in the same

atom can have the same set of
4 quantum numbers.

That is, each electron in an atom has

a unique address of quantum
numbers.
 11
Electrons
Electrons in
in Atoms
Atoms

When n = 1, then l = 0 (s)

this shell has a single orbital (1s) to which 2e-
can be assigned.
When n = 2, then l = 0, 1 (s, p)
2s orbital 2e-
three 2p orbitals 6e-
TOTAL = 8e-
 12
Electrons
Electrons in
in Atoms
Atoms

When
Whennn==3,
3,then
thenll==0,
0,1,
1,22(s,
(s,p,
p,d)
d)
3s
3sorbital
orbital 2e-
2e-
three
three3p
3porbitals
orbitals 6e-
6e-
five
five3d
3dorbitals
orbitals 10e-
10e-
TOTAL
TOTAL == 18e-
18e-
 13
Electrons
Electrons in
in Atoms
Atoms

And
Andmany
manymore!
more!
When n = 4, then l = 0, 1, 2, 3 (s,p,d,f)
4s orbital 2e-
three 4p orbitals 6e-
five 4d orbitals 10e-
seven 4f orbitals 14e-
TOTAL = 32e-
Principal # of Name of # of # of Total # of
quantum subshells subshell orbitals electrons electrons
# (n)
1 1 1s 1 2 2
2 2 2s 1 2 8
2p 3 6
3 3 3s 1 2 18
3p 3 6
3d 5 10
4 4 4s 1 2 32
4p 3 6
4d 5 10
4f 7 14
14
15
Describing the shapes of the s and p orbitals

10/6/2015
• S orbitals are spherical. For example, 1s orbital

• The 2s orbital is also spherical as the 1s but is at a higher energy

level than the 1s orbital.

16
 17
Describing the shapes of
the s and p orbitals

P orbitals are dumbbell in shape

with the nucleus located between
the two halves of the dumbbell.
Relative energies of orbitals

10/6/2015
( s < p < d < f)

Note,
There is an irregularity in the position of the 3d and 4s
orbitals. The 3d orbitals have slightly more energy than
the 4s therefore the 4s orbitals fills first then the 3d
orbitals followed by the 4p orbitals

18
 Electronic configuration

10/6/2015
 Electronic configuration describes the arrangement of electrons in orbitals of an atom.
The electronic configuration can be worked out as follows:

 Electrons are added to an atom, one at a time, starting with the lowest energy orbital (aufbau
principle)

 No more than two electrons can occupy an orbital (pauli exclusion principle)

 Electrons fill degenerate orbitals one at a time with parallel spin before
19 a second electron is added
with opposite spin (hund’s rule)
Electronic configuration

10/6/2015
 Hund’s rule: When filling sublevels other than s, electrons are placed in individual
orbitals before they are paired up.

 Pauli’s exclusion principle: When we draw electrons, we use up and down arrows.
So, if an electron is paired up in a box, one arrow is up and the second must be
down.

 Aufbau Principle - electrons fill orbitals starting at the lowest

20 available energy state
before filling higher states (1s before 2s).
 21
Filling Orbitals

 Electrons fill orbitals of different energies by filling the lowest energy

first.

 This is known as the building up principle or the Aufbau principle

 22

Electron
Filling
Order
Shell and Subshell
Structure 23
Atomic Energy Levels
according to the
(n + l) rule

Buildup (aufbau) Principle

 24
Writing
Writing Atomic
Atomic Electron
Electron Configurations
Configurations

Two
Two ways
ways ofof writing
writing
configs.
configs. One
One isis spdf notation
called the spdf
called the spdf for H, atomic number = 1
notation.
notation. 1 no. of
1s electrons

value of l
value of n
Write the EC of P 3-: Z=15
Write the EC of Ca: Z=20
Write the EC of Sc: Z=21
 28
Writing
Writing Atomic
Atomic Electron
Electron Configurations
Configurations

Two
Two ways
ways of of
writing
writing configs.
configs. ORBITAL
ORBITALBOX BOXNOTATION
NOTATION
for
forHe,
He, atomic
atomic number
number== 22
Other
Other isis called
called
the Arrows
Arrows
the orbital
orbital box
box 22 depict
notation.
notation. 11 ss depict
electron
electron
1s spin
spin
1s

One electron has n = 1, l = 0, ml = 0, ms = + 1/2

Other electron has n = 1, l = 0, ml = 0, ms = - 1/2
 Orbital box Notation

 So how do electrons fit into an orbital?

 Electrons are negatively charged, and so repel one another. An electron also has
property called spin. The two electrons in an orbital have opposite spins, helping to
counteract the natural repulsion between negative charges.

Chemists often represent an orbital as a box that can hold up to 2 electrons.

• Each electron is shown as an arrow, indicating its spin: either or
• Within an orbital, the electrons must have opposite spins
Classification of orbitals of a many electron atom according
30
to their energies.

Orbitals with same value of n and different value of l comprise a shell.

Example: 2s and 2p comprise a shell.

A group of orbitals with exactly equal energies comprise a subshell.

Example: 2px, 2py and 2pz

The orbital approximation ignores electron-electron repulsion but takes into account
Hund’s rule: electrons with parallel spins () tend to stay apart compared to electrons
with antiparallel spins ().
Electronic structure and the periodic table
31
Electrons in the outermost shell of an atom are the most important in
determining chemical properties. Chemical reactions involve only the outer
(valence) electrons. The inner (core) electrons are not involved in chemical
reactions.

Elements in a given vertical column (families) of the periodic table have

similar outer-shell electron configurations and similar properties. They
are isoelectronic with respect to the number of valence electrons.

Elements in a row show regular trends in their properties due to the

continuing increase in the number of valence electrons until a shell is
filled.
Constructing the periodic table by filling orbitals with electrons (electron
configurations). 32
Construction of the first row of the periodic table.
Electron configurations: 1H and 2He.

Aufbau: Fill 1s orbital first

Pauli: no more than two
electrons in the 1s orbital
The basis of the duet rule: filling
a shell
1s subshell filled with 2He =
stable electron core given
symbol [He].
Filling the orbitals of 3Li, 4Be and 5B

33
Aufbau: Fill 1s orbital first, then 2s, then
2p.
Pauli: no more than two electrons in the 1s
orbital.

2s subshell filled with 4Be.

Filling the orbitals of 6C and 7N. The need for a third rule
(Hund’s rule): 34
For carbon, how do the two 2p
electrons distribute themselves in the
three 2p orbitals?

For nitrogen, how do the three 2 p

electrons distribute themselves in the
three 2p orbitals?
 Hund’s rule: Applies when filling the orbitals of a subshell with electrons. Or more
generally when filling orbitals of identical energy 35

When adding electrons to a subshell, the ground state electronic configuration is formed by
maximizing the number of electrons with parallel spins ()() before pairing two electrons in
one orbital ().

Example: 6C = [He]2s22px()2py()2pz() = ground state

Example: 6C = [He]2s22px()2py()2pz() = excited state

Filling the orbitals of 6C and 7N. The need for a third rule
(Hund’s rule): 36

Hund’s Rule: When electrons occupy

orbitals of the same energy, the lowest
energy state corresponds to the
configuration with the greatest number of
orbitally and spin unpaired electrons.

When the configuration is

written as 1s22s22p2 it is
understood that two different p
orbitals are occupied.
 37
Summary: Electron
configurations
from 1H to 10Ne.

No new features for

the electron
configurations from
11
Na to 18Ar.
 The third full row of the periodic table: 19K-36Kr
38
The 4s and 3d orbitals are close in energy in the one electron atom. Difficult to
predict stability for multielectron atom.

The 4s orbital is slightly more

stable than the 3d orbital at the 19
K = [Ar]4s13d0
beginning of the third full period 20
Ca = [Ar]4s23d0
of the periodic table:

The reason is that the 4s orbital has a higher probability of being closer to the
nucleus and see a greater effective Z eff than a 3d orbital.
 Electron configuration of the transition elements:
21
Sc through 30Zn
39
d orbitals raise their ugly heads!

21
Sc, 22Ti, 23V, 24Cr, 25Mn, 26Fe, 27Co, 28Ni, 29Cu, 30Zn

19
K = [Ar]4s1
20
Ca = [Ar]4s2

What would you expect for 21Sc?

21
Sc = [Ar]4s23d1. Not quite correct….

The 3d electron is lower in energy than the 4s electron in 21Sc from experiment:
21
Sc = [Ar] 3d14s2
 Ground State Electron Configurations
ORBITALS and Hund’s Rule 40
41
42