FS 0111: General Chemistry

Lecture 1B: Electronic configuration & Quantum

numbers

Dr. Malima M Nyemaga

 Learning Outcomes
 Understand the general idea of the quantum mechanical description of electrons
in an atom.

 To apply the results of quantum mechanics to chemistry.

 List and describe traits of the four quantum numbers that form the basis for
completely specifying the state of an electron in an atom.

 To understand the 3D representation of electronic orbitals.

 Derive the predicted ground-state electron configurations of atoms

 Identify and explain exceptions to predicted electron configurations for atoms and
ions
 Electronic Structure of Atoms
Historical perspective
Atomic structure
Atomic spectra Quantum theory • Dalton, 1803
• Bunsen, Kirchhoff, • Plank,1900  atomic nature
1860  Black body radiation • Faraday, 1834
 1st spectroscope • Einstein, 1905  Electricity & Mag.
 1st line spectrum  Photoelectric effect • Thompson, 1807
• Lockyer, 1868  electrons e/m
 He in solar system • Millikan, 1911
• Balmer,1885 • Bohr, 1913  oil drop
 H line spectrum
 Applied to atom • Rutherford, 1911
structure  gold foil/nucleus
 Quantum mechanics
• Each electron can be explained using a standing wave
equation (wave function).

• Quantized frequency corresponds to quantized energy

(Debroglie, Plank, etc.).

• Integer values are critical to this description: quantum

numbers.
 Quantum mechanics
y Examples of wave equations

y = sinx Propagating wave

x


2 px
Y= sin
l l Standing wave
x
l = 1/2l
nO = frequency
nodes = 2
l
 Quantum mechanics
• Using math we do NOT want to deal with, you can do the same
thing for an electron in hydrogen.

1 -r
Y= e
p
r
• But what, physically is ? What is waving?

• Born (1926): 2= probability/volume of finding the electron.

 Quantum mechanics
• Plot of 2 for hydrogen atom.

• The closest thing we now have to a

physical picture of an electron.

• 90% contour, will find electron in

blue stuff 90% of the time.
 Quantum mechanics
• The wave equation is designated with
a lower case Greek psi ().

• The square of the wave equation, 2,

gives a probability density map of
where an electron has a certain
statistical likelihood of being at any
given instant in time.
 Atomic orbitals
• An orbital: The space around the nucleus of an atom where
there is maximum probability of finding an electron.

• We cannot know precisely where the electron is at any

moment, but we can describe where it probably is, i.e. where it
is most likely to be found, or where it spends most of its time.

• Although the wave function (atomic orbital) has no physical

meaning, we do ascribe a physical meaning to the square of a
wave function, ᵠ2.
 Atomic orbitals
• This quantity expresses the probability that the electron is at
a particular point (or, more precisely, in a particular very
small volume) within the atom.
• The wave function ᴪ is a mathematical description of the
motion of the electron’s matter-wave in terms of time and
position.
• The Hamiltonian operator, represents a set of mathematical
operations that, when carried out on a particular ᴪ, yields an
energy state.
 Quantum Numbers
• Solving the wave equation gives a set of wave functions, or
orbitals, and their corresponding energies.
• Each orbital describes a spatial distribution of electron density.
• An orbital is described by a set of three quantum numbers
(integers).
Why three?
• 3 dimensions
• Need three quantum numbers to define a given wave function.
• Another name for wave function: Orbital (because of Bohr).
 Quantum Numbers
• Quantum numbers: Numbers which are required to
describe the distribution of electron in atoms.
• They are derived from mathematical solution of the
Schrodinger equation for the hydrogen atom.
• Three of the four quantum numbers specifies the
atomic orbital of an atom.
• The fourth is needed to label an electron in atomic
orbital.
 Principal Quantum Number, n
• It describes the energy level on which an orbital
resides.
• The values of n are integers > 0, i.e. Positive integer
from 1, 2, 3…….
• Largest energy difference is between energy levels.
• It also relates to the average distance of an electron
from the nucleus in a particular orbital. i.e. indicates
the relative size of the orbital.
 Azimuthal Quantum Number, l
• Also called angular momentum quantum number or orbital
shape quantum number .
• Defines shape of the orbital.
• Allowed values of l are integers ranging from 0 to n-1.
• It is limited by n.
• The number of possible l values equals the value of n.
• We use letter designations to communicate the different
values of l and, therefore, the shapes and types of orbitals.
 •
Azimuthal Quantum Number, l (l = 0,1..., n-1)
The value of l is generally designated by the letters s, p, d, f, as
follows, and each of these letters corresponds to a shape of orbital.
Values of l 0 1 2 3 4 5
Name of orbitals s p d f g h

• The unusual sequence of the letters (s, p and d) has a

historical origin.
• They are related to emitted spectral lines with particular energy
states which were found to be sharp, principal, and some were
diffuse and others were fundamentals.
 Azimuthal Quantum Number, l
• Orbitals with the same value of n form a shell.

• Different orbital types within a shell are subshells (s, p, d, f).

E.g. the shell with n = 2 is composed of two subshells, 0 and 1
(the allowed values for n = 2).

• These subshells are called 2s and 2p subshells where 2

denotes the value of n, and s and p denotes the values of l.
 Magnetic Quantum Number, ml
• Describes the three-dimensional orientation of the orbital in
space.
• It is sometimes called the orbital-orientation quantum number.
• Values are integers ranging from -l to l; −l ≤ ml ≤ l.
• The number of possible values equals the number of orbitals in
a subshell with particular value which is given by 2l + 1
• Note: the total number of orbitals for a given n value is n2. The
total number of electrons = 2n2
• Practice Question: Specify the l and ml values for n = 4.
Relation Between Quantum Numbers & Atomic Orbitals
Relation Between Quantum Numbers & Atomic Orbitals

 m
Shapes of Atomic Orbitals
 s Orbitals
 Value of l = 0.
s -orbitals
 Spherical in shape.

 Radius of sphere
increases with
increasing value of n.
 s Orbitals

 s orbitals possess n-1 nodes, or regions where there is 0

probability of finding an electron.
 p Orbitals
• Value of l = 1.
• Have two lobes (of high probability) with a nodal plane
between them.
• One on either side of the nucleus.

Note: Always 3 p orbitals for a given n.

 p Orbitals
• The nucleus lies at the nodal plane of this “dumbbell-shape”.
• The one closest to the nucleus is the 2p orbital and that one p orbital
consists of two lobes and that the electron spends equal time in
both.
• Unlike the s orbital, p orbital (ml = -1, 0, +1) has a specific
orientation in space, which are mutually perpendicular to each other.
• They are identical in size, shape, and energy, differing only in
orientation.
 d Orbitals
 An orbital with l = 2 is
called the d-orbital.
 2 nodal planes
 Four of the five orbitals have
4 lobes; the other resembles
a p orbital with a doughnut
around the center.
 The d-orbital can have any
one of the five orientations
Note: Always 5 d orbitals for a given n. as ml = -2, -1, 0, 1, and 2.
 d Orbitals
d orbitals
• Four of the five d orbitals have
four lobes (“cloverleaf shape”)
prescribed by two mutually
perpendicular nodal planes, with
the nucleus lying at the junction
of the lobes.
• The 5th d orbital, dz2 has a
different shape: two major lobes
lie along the z axis, and a donut-
shaped region of electron density
girdles the center.
 Orbitals & Nodes
Orbital Symmetry Node geometry Spherical nodes/shell* Orbitals/set

s spherical spherical n-1 1

p cylindrical 1 planar n -1 3
around x, remainder
y, or z axis spherical

d complex 2 planar surfaces n -2 5

diagonal to
Cartesian axis;
remainder spherical

f complex complex n –3 7

* n = the shell, with n = 1 the ground state or lowest possible energy shell. Thus n may have integral
values from 1 - infinity.
 Energies of Orbitals

• For a one-electron hydrogen

atom, orbitals on the same energy
level have the same energy.

• That is, they are degenerate.

Energies of Orbitals
• As the number of electrons
increases, though, so does
the repulsion between them.

• Therefore, in many-electron
atoms, orbitals on the same
energy level are no longer
degenerate.
Energies of Orbitals
• For a given energy level (n):
• Energy: s<p<d<f
• s lowest energy, where
electrons go first.
• Next p
• Then d
Why?
 Energies of Orbitals

The closer to the nucleus, the lower the energy

 The problem with quantum mechanics
 It’s not hard to solve equations for the various wave functions if
they are all alone (like H)
 The problem is what happens in the presence of other
electrons.
 The electron interaction problem.
 Electron interaction so complex, exact solutions are only
possible for H!
 Electron probabilities overlap a lot, must interact a lot, repulsion
keeps them from ever “touching”
 Spin Quantum Number, ms
• A fourth dimension required. Why?
• Time. Adding time changes E.
• Another integer (quantum number) needed.
• Time dependent Schrodinger equation.
• This leads to a fourth quantum number,
the spin quantum number ms.
• The spin quantum number has only 2 values
+1/2 and -1/2.
• Describes magnetic field vector of electron
(i.e. is used to specify an electron’s spin).
 Electronic Configuration of Elements

• Describes how electrons are distributed in its atomic orbitals.

• Follows a standard notation in which all electron-containing

atomic subshells (with the number of electrons they hold written
in superscript) are placed in a sequence.
 Electron Configurations
 Shows the distribution of all electrons in an
atom.
• Name of each electron is unique.
• Name consists of four numbers: n, l, ml, ms.

4p 5  Electronic configuration consist of:

Number denoting the energy level.
Letter denoting the type of orbital.
Superscript denoting the number of
electrons in those orbitals.
Rules for Writing Electron Configuration
• There are THREE rules that govern the assignment of
electron configurations and orbital notations.
1. Pauli’s exclusion principle
2. Hund's rule (of maximum multiplicity)
3. Aufbau principle
‘No two electrons in the same atom
can have the same four quantum
numbers.’
“No two electrons in the same atom
can have exactly the same energy”.
To occupy the same orbital, the two
electrons must spin in opposite
directions (paired spins).
 • When orbitals of equal energy
are available, the electron
configuration of lowest energy
has the maximum number of
unpaired electrons with
NOT: parallel spins’.
• The most stable arrangement
of electrons is one with the
maximum number of unpaired
electrons’.
 Hund’s Rule
• It minimizes electron-electron repulsions and stabilizes the
atom.
• Electrons will fill an orbital singly, before pairing up in order to
minimize electron-electron repulsions.
• Electrons that are single occupants of orbitals have parallel
spins and are assigned an up arrow.
• The second electron to enter the orbital, thus forming an
electron pair, is assigned a down arrow to represent opposite
spin.
 Aufbau Principle

“Lower energy orbitals fill before proceeding to higher energy

orbitals”

• Electrons are added one at a time to the lowest energy

orbitals available until all the electrons of the atom have
been accounted for.
• Use the diagonal rule as the map to determine the outermost
or valence electron configurations for any of the elements.
 Aufbau Principle
1s

2s 2p

3s 3p 3d

4s 4p 4d 4f

5s 5p 5d 5f

6s 6p 6d
2 2 6 2 6 2 10 6 2 10
7s 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d …
A vertical orbital diagram
for the Li ground state
Empty

Sublevel energy increases

Half-filled
from bottom to top

1s22s1

Filled, spin-paired
 Determining Quantum Numbers from Orbital Diagrams

PROBLEM: Write a set of quantum numbers for the third electron and a set for the
eighth electron of the fluorine (F) atom.
PLAN: Use the orbital diagram to find the third and eighth electrons .

9F
Up arrow = +1/2
Down arrow = -1/2
1s 2s 2p

SOLUTION: The third electron is in the 2s orbital. Its quantum numbers are:

n= 2 l= 0 ml = 0 ms= +1/2

The eighth electron is in a 2p orbital. Its quantum numbers are:

n=2 l= 1 ml = -1 ms= -1/2

Condensed ground-state electron configurations in the
first three periods
 Categories of Electrons

Inner (core) electrons: fill all the lower energy levels of an atom

Outer electrons: those electrons in the highest energy level

(highest n value) of an atom

Valence electrons: those involved in forming compounds; the bonding

electrons; among the main-group elements, the valence electrons
are the outer electrons
 General Observations about the Periodic Table

A. The group number equals the number of outer electrons (those with
the highest value of n) (main-group elements only)

B. The period number is the n value of the highest energy level.

C. The n value squared (n2) gives the total number of orbitals in that
energy level; 2n2 gives the maximum number of electrons
in the energy level.
 Application of Diagonal Rule
• Using the diagonal rule, determine the electron configuration for
the outermost valence electron in sulphur.

• Sulphur has atomic number (proton number) 16 which is equal

to 16 electrons in neutral atomic suphur .
• Thus, the electron configuration of sulphur is 1s22s22p63s23p4.

Practice: Write the electron configuration of elements in the

periodic table.
 Noble Gas Configuration
• The electron configurations of all elements except hydrogen
and helium can be represented using a noble gas core.

• Noble gases include : He Ne Ar Kr Xe Rn

• The electron configuration of potassium (Z=19) is
1s22s22p63s23p64s1.

• Because 1s22s22p63s23p6 is the electron configuration of argon,

we can simplify potassium’s electronic configuration to [Ar]4s1.
 Noble gas configuration
• Aufbau tells us that all lower sublevels MUST be filled before
filling sublevels of higher energy.

• This results in us writing the same information repeatedly when

making short hand configurations:
Mn 1s22s22p63s23p64s23d5
Cl 1s22s22p63s23p5
Ca 1s22s22p63s23p64s2
 Noble Gas Configuration
• Rules: Choose the largest noble gas that has an atomic number
LESS than the element you are working with.
• For Mn, the largest noble gas is Ar.
• Because we know that lower sublevels are already filled, we
can substitute part of the configuration with a noble gas:
Mn 1s22s22p63s23p64s23d5
Ar 1s22s22p63s23p6
Therefore we write: [Ar] 4s23d5
 Noble Gas Configuration
•Now
Nowtry
tryititfor
forClCl
Cl 1s22s22p63s23p5

The largest noble gas is Ne 1s22s22p6

[Ne] 3s23p5
Valence electrons – these ARE used in bonding
Core electrons – these are NOT used when bonding

55
 Exceptional Configurations (Exceptions to Aufbau)
•Now try itisfor aCl general stability associated with electron
There
configurations.

 Filled sublevels are MOST stable.

 Half filled sublevels are stable.
 All other configurations for sublevels are LEAST stable.
There are several notable exceptions to the order of electron
filling for some of the transition metals.

56
 Exceptional Configurations (Exceptions to Aufbau)
•Now try it forby
Sometimes Cl moving electrons between sublevels that are
close in energy, atoms can achieve a more stable
configuration.

Examples include: s2d4

• Chromium (Z = 24) is [Ar] 4s13d5 and not [Ar] 4s23d4 as
expected.
Because d5 is half filled and more stable, the atom takes on the
configuration of s1d5

57
 Exceptional Configurations (Exceptions to Aufbau)
•CrNow[Ar]
try it4sfor
13dCl
5

Mo [Kr] 5s14d5

W [Xe] 6s14f145d5

58
 Exceptional Configurations (Exceptions to Aufbau)
•• Now try itexception
Another for Cl occurs with the configuration: s2d9
• Copper (Z = 29) is [Ar]4s13d10 and not [Ar]4s23d9 as expected.
• Again, by moving 1e- from the “s” sublevel to the “d” sublevel,
the “d” sublevel becomes filled, s1d10
Cu [Ar]4s13d10

Ag [Kr]5s14d10

Au [Xe]6s14f145d10
59
 Exceptional Configurations (Exceptions to Aufbau)

• The reason for these anomalies is the slightly greater stability of

d subshells that are either half-filled (d5) or completely filled
(d10).

 Exceptional configurations only happen between “s” and “d”

sublevels….NEVER between “s” and “p” sublevels.
 Exceptional Configurations (Exceptions to Aufbau)

The Period 4
crossover in
sublevel energies
Unusual electron configurations
 Determining Electron Configuration

Using the periodic table, give the full and condensed electron configurations, partial orbital
diagrams showing valence electrons, and number of inner electrons for the following elements:

(a) potassium (K: Z = 19) (b) molybdenum (Mo: Z = 42) (c) lead (Pb: Z = 82)

SOLUTION:

(a) for K (Z = 19)

full configuration: 1s22s22p63s23p64s1

condensed configuration: [Ar] 4s1
K has 18 inner electrons.
partial orbital diagram:

4s1
(b) for Mo (Z = 42)

full configuration: 1s22s22p63s23p64s23d104p65s14d5

condensed configuration: [Kr] 5s14d5
partial orbital diagram: Mo has 36 inner electrons
and 6 valence electrons.

5s1 4d5

(c) for Pb (Z = 82)

full configuration: 1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p2
condensed configuration: [Xe] 6s24f145d106p2
partial orbital diagram:
Pb has 78 inner electrons
and 4 valence electrons.

6s2 6p2