Lecture 1:

1. Discovery of the electrons and nucleus

2. Theories of atomic structure
3. The classical description of the atom
 The results and limitations of the atomic
theory of Bohr’s
1. The Bohr theory satisfactorily explained the
spectra of hydrogen and other species having one
electron (He+, Li2+)
2. Could not explain the spectra of more complex
species
3. The theory of Bohr’s could not mention in wave
nature of the electron, so the Bohr assumption of
circular orbits of the electron in the atom was failed
➢ The classical mechanics could not solve a problem
with small particles. To deal with this problem, it is
necessary to use a new physics, quantum mechanics
Lecture 2:
1. The quantum mechanics picture of the atom
2. The solution of the Schrodinger equation for H
atom
3. Physical meaning and values of quantum numbers
1.3. The principles of quantum mechanics
1.3.1.Wave-particle duality of matter and
radiation
1887-1927 experiments were done.
Light as a wave
Light is one type of electromagnetic radiation (the
periodic variation of an electric field )
1.3. The principles of quantum mechanics
The wave properties of an electromagnetic radiation
can be characterized by means of:
-Wavelength (): the distance between identical
points on successive waves (the wave travels during
one cycle).
Unit: m, nm (10-9m), pm (10-12m)
- Frequency (υ): is the number of cycles the wave
undergoes per second and is expressed in units of
l/second [s-1 ; also called hertz (Hz)].
1.3. The principles of quantum mechanics

For a wave, traveling at some speed, the wavelength

and the frequency are related to each other by:
υ= c
In a vacuum, all types of electromagnetic radiation
travel at 2.997x108 m/s, called the speed of light
1.3. The principles of quantum mechanics
Light as a particle
The photoelectric effect
A beam of light hitting a metal surface can eject electrons
Ei < ϕ Ei ≥ ϕ K.E = Ei - ϕ

Metal

The energy of an incoming photon (Ei= hυ must be equal or greater

than the work function of the metal in order to eject an electron)
Einstein confirm that both descriptions (wave and
particle) can coexist without a contradiction
1.3. The principles of quantum mechanics
1.3.2. The wave nature of the electron
➢ Why is the electron in a Bohr atom restricted to
orbiting the nucleus at certain fixed distances?
For a decade no one, not even Bohr himself,
had a logical explanation
➢ In 1924 Louis De Broglie (PhD thesis, Nobel
Prize 1929) postulated that:
just as light has wave-like and particle-like
properties, matter (electrons) must also be both
wave-like and particle-like properties
1.3. The principles of quantum mechanics
1.3.2. The wave nature of the electron
➢ De Broglie deduced that the particle and wave
properties are related by the expression:

h λ- wavelength of a moving
λ= (1.2) particle; m- its mass; v- its
mv velocity

Equation (1.2) implies that a particle in

motion can be treated as a wave
• Later the prediction of de Broglie was confirmed
by, Clinton Davisson and Lester Germer in the US
and Thomson in England (showed that electrons
possess wavelike properties).
• A beam of electrons passing through a thin piece
of Aluminum. The patterns are similar to those
observed with X rays (which are waves).

• Whether the de Broglie equation is true for

every moving particle or not ?
•Calculate the wavelength of an electron traveling at
1.24x107 m/s. me = 9.1x10-31 kg (λ = 5.87x10 m)
-11

•Calculate the wavelength of a baseball of mass 149g

traveling at 41.3m/s (λ = 1.08x10 m)
-34

✓Wave properties of macroparticles can be rejected

- Electrons have both wave-like and particle-like
properties
- If particles like e have wave properties what is the
equation of the motion of an e?
1.3.3. The uncertainty principle

One of the underlying principles of quantum mechanics

Given in 1927 by Heisenberg that is consistent with the
experimental observations
Statement:
It is impossible to determine accurately both the position
and the velocity of an electron (or any other small particle)
simultaneously. The mathematical expression is:
Δx and Δvx are uncertainties in
h
Δx.Δv x  (1.3) position and velocity
m
Δx smaller, Δvx larger and
vice versa
1.3.4. The quantum mechanics picture of the atom
1. Wave function:
The wave function is different for various points of
atomic space. Mathematically it is written as the
equality  = (x,y,z), Where x, y, z are the co-ordinates
of a point
+ Its square 2 characterises the probability of
finding the electron at a definite point in atomic space
+ The value of 2 dV is the probability of finding the
electron in an element of volume dV
2. Schrodinger equation

1927 Erwin Schrodinger wrote an equation of

motion for particles (like electrons) that account for
their wave-like properties.

(1.4)

E is the full energy of the electron;

H is Hamiltonian operator
Ψ- wavefunction (describes the particles)
For the H atom, where the potential energy is a
function of one distance variable, r

It simplifies the equation to use the spherical polar

coordinates.
The wavefunction of the electron in an H is written as a
function of r, θ , Ф: ψ (r, θ , Ф)
1.3.3. The quantum mechanics picture of the atom
1.4. The solution of the Schrodinger equation for H atom

1.4.1. The binding energy En of the electron to the

nucleus for H atom:

n – integer, 1, 2, 3…

Key idea: binding energy can be quantized

The principle quantum number n, come out of solving the
Schrödinger equation.
∞
Note:
- All binding energies are negative
- Negative energy means that the electron is
bound to the nucleus.
- At n= ∞, En = 0, the e is free from the
nucleus
- The lowest (most negative) energy is called
the ground state
+ The ground state is the most stable state
+ The ground state is the n =1 state
1.4.2. Wavefunction (orbitals) for H atom
When solving Hψ= Eψ the solutions are En and
ψ(r,θ,ϕ)
ψ(r,θ,ϕ)- stationary wavefunction, time-independent
In solution ψ(r,θ,ϕ), two new quantum numbers
appear!
A total of 3 quantum numbers are needed to
describe a wavefunction in 3D.
1. Principle quantum number n
n = 1, 2, 3… … ∞, determines binding energy
2. Angular momentum quantum number l
l is related to n, for a given value of n
l has possible integral values of 0 to n-1
It determines angular momentum (shape of orbital)
3. Magnetic quantum number ml
ml is related to l, for a given value of l.
ml receive the values: -l,…,0….., +l
determines behavior of atom (orientation of the orbital) in
magnetic field
➢ To completely describe an orbital, we need to use all three
quantum numbers: Ψn,l,m(r,θ,φ)
The wavefunction describing the ground state is: ψ100

An orbital is the spatial part of a wavefunction;

n(shell) l(subshell) m(orbital)
l =0 ⇒ s orbital
l =1 ⇒ p orbital
l =2 ⇒ d orbital
l =3 ⇒ f orbital

for l =1: m = 0 __pz__ orbital,

m = ±1 states combine to give _px_ and __py__ orbitals
 100 1s

200 ψ200 2s -RH/22

21+1 Ψ21+1 2px(2py) -RH/22

2pz)

2px(2py)

Degenerate- having the same energy

 3s 3px 3pz 3py 3dxy 3dyz 3dz2 3dxz 3dx2-y2

2s 2py 2pz 2py

1s
1.4.3. Shapes of H-atom wavefunctions
S orbitals
[ Ψnlm(r,θ,φ)]2 = PROBABLITY DENSITY- probability of
finding an electron per unit volume at r, θ, φ
Ψnlm=Rnl(r).Ylm(θ, ϕ)
Rnl(r) radial wavefunction; Ylm angular wavefunction

Bohr radius 0.529 Ǻ

constant
θ ϕ
Probability density plot of s orbital

r
p orbitals
p wavefunctions have θ and ϕ dependance.
p orbitals are not spherically symmetrical
p orbitals consist of two lobes (of opposite sign) separated
by a nodal plane on which ψ (and ψ2 = 0)

There is zero probability of finding a p electron in a nodal

plane. Thus there is no probability of finding a p-electron at
the nucleus
Probability density maps of p orbitals

Highest prob. Along z axis along x along y

Nodal plane θ =90o Nodal plane ϕ=90o Nodal plane ϕ=0o
d- orbitals
1.4.4. Physical meaning and values of quantum numbers
1. The principle quantum number n
✓Determines the energy level or shell of an orbital
✓It may have only integral values n = 1, 2, 3, 4,…
✓As n increases, the energy of the electron increases
n 1 2 3 4 5 6 7
Energy level K L M N O P Q
2. The angular momentum quantum number l
✓Designates the shapes of the orbitals
✓The values of l depend on the value of the principle
quantum number n. l has possible integral values from 0
to (n-1)
✓The value of l is generally designated by the letters s,
p, d, f, g…as follows

l 0 1 2 3 4 5

Name of orbitals s p d f g h
✓A collection of orbitals with the same value of n is
called a shell. One or more orbitals with the same n
and l values are referred to a subshell.
✓The designation of a subshell includes two parts
+ The first part is the value of n
+ The second part is the letter corresponding to the
value of l
Exampels:
* The shell with n=2 is composed of two subshell, l=0
and l=1 (2s and 2p)
* The shell with n =3 is composed of three subshells,
l=0, l=1, and l=2 (3s, 3p, 3d)
3. The magnatic quantum number ml
✓Describes the orientation of the orbital in space
✓For a certain value of l, there are (2l+1) values of ml as folllows:
- l,....., 0, ......+l
If l=0, ml = 0, but l=0 corresponds to the s orbital
If l=1, then there are three values of ml: -1, 0, +1 Thus the p
orbital has three orientations in the space: px, pz, py
If l=2, there are five values of ml:-2, -1, 0, +1, +2
l=2 corresponds to the d orbital, so the d orbital has five
orientations in the space
l=2 (ml=1; 2): dxy; dyz; dzx; dx2-y2
l=2 (ml= 0): dz2
4. The electron spin quantum number ms
ms referrs to the spin of an electron and the orientation
of the magnetic field produced by this spin.
The quantum number ms was introduced to make
theory consistent with experiment
For every set of n, l, ml values, ms can have the value
of +1/2 (clockwise) and -1/2 (counterclockwise)
 Fig. 4. Orbital energy levels for the hydrogen atom

Excited states

Ground state

The energy of an electron in a hydrogen is dependent on

its principle quantum number n.
Thus, the energies of hydrogen orbitals increase as
follows: 1s < 2s=2p<3s=3p=3d<4s=4p=4f<...