PHY 310

MODERN PHYSICS

ATOMIC STRUCTURE AND ENERGY

LEVELS IN AN ATOM
 OUTLINE
4.1 Thomson’s model, Rutherford’s model
4.2 The Bohr model of the hydrogen atom
4.3 Bohr’s postulate
4.4 Emission and absorption line spectrum of hydrogen gas
4.5 Evidence of quantized energy level : Line spectrum of
various gases, Frank-Hertz experiment
OUTLINE

4.6 Radius of the Bohr orbit

4.7 Energy of quantum state, n of the hydrogen atom
4.8 Energy of quantum state, n of the an atom
4.9 The energy level diagram
4.10 Concept of ionization and excitation
 Frank and Hertz
Experiment
1914-
Demonstrated

DISCOVERY TIMELINE the existence of

excited states in
mercury atoms,
confirm the
JJ Thomson quantum theory
1897- of electrons
Discovered occupied only
electron and discrete,
plum pudding quantized
atom energy states.

Ernest Neil Bohr 1922

Rutherford – Proposed
1911 – outer shell held
Discover atomic more than inner
nucleus and shell
proton
FIRST THOUGHTS: BEGINNING HISTORY OF THE ATOM
Some of the early philosophers thought that matter was
composed of tiny particles. They reasoned that you could take
a piece of matter, cut it in half, and continue to cut again and
again. Eventually, you wouldn't be able to cut any more. You
would have only one particle left. They named these particles
atoms.
The early philosophers didn't try to prove their theories by
doing experiments as scientist now do. Their theories were the
result of reasoning, debating, and discussion—not of evidence
or proof. Today, scientists will not accept a theory that is not
supported by experimental evidence.
REVOLUTION OF ATOM DISCOVERY
 Experiment using
Cathode-Ray tube
THOMSON’S EXPERIMENT The electrons were deflected up
when upper plate is charged
positively and deflected down when
upper plate is charged negatively.
THOMSON’S MODEL
❑He knew that opposite charges attract each other.
❑He observed that these particles were attracted to
the positively charged anode, so he reasoned that
the particles must be negatively charged.
❑These negatively charged particles are called
electrons.
❑If atoms contain one or more negatively charged
particles, then all matter, which is made of atoms,
should be negatively charged as well.
❑But all matter isn't negatively charged.
THOMSON’S MODEL CONT.
❑Could it be that atoms also contain some positive
charge?
❑The negatively charged electrons and the unknown
positive charge would then neutralize each other in the
atom, so the atom is neutral.
❑Thomson revised Dalton's model of the atom.
❑Thomson pictured a sphere of positive charge.
❑The negatively charged electrons were spread evenly
among the positive charge.
❑Thomson believed that the electrons were like plums
embedded in a positively charged “pudding,” thus it was
called the “plum pudding” model.
 Thomson's atomic mo
RUTHERFORD’S MODEL del failed to explain
1) how the positive
charge holds on the
electrons inside the
atom.
2) the atom's stability.
 In 1906, Ernest Rutherford and his
coworkers began an experiment to
RUTHERFORD’S MODEL find out if Thomson's model of the
atom was correct.
Rutherford’s Experiment:
prediction
Alpha particles will pass
through like this …

12
RUTHERFORD’S EXPERIMENT: WHAT
ACTUALLY HAPPENED

13
WHAT’S GOING ON?
Most alpha particles went straight
through, and
some were deflected,
BUT
A few (1 in 20,000) reflected
straight back to the source!

“It was quite the most incredible event that has ever happened to
me. It was almost as incredible as if you had fired a fifteen inch
shell at a piece of tissue paper and it came back and hit you.”
14
THE NUCLEUS REPELS ALPHA PARTICLES

15
RUTHERFORD’S MODEL CONT.
Thomson model Fail Rutherford’s new model of the
atom fits the experimental data
This nucleus that
If contained most of the
Thomson mass of the atom
was right, caused the deflections
the model that were observed in
would his experiment.
look Therefore,
like… Rutherford’s model of
the atom is mostly
empty space.
 RUTHERFORD’S MODEL CONT.
❑Rutherford hypothesized that almost all the
mass of the atom and all of its positive
charge are crammed into an incredibly small region of space at the
center of the atom called the nucleus.
❑In Rutherford's model, the only other particle in the atom was the
proton.
❑That meant that the mass of an atom should have been approximately
equal to the mass of its protons. However, it wasn't.
❑The mass of most atoms is at least twice as great as the mass of its
protons.
❑He also predict the present of another particle with unit mass but
having no charges. He name that particle as neutron.
EXAMPLE 1
In Rutherford’s planetary model of the atom, what
keeps the electrons from flying off into space?

Answer:
In Rutherford’s planetary model of the atom, the Coulomb force
keeps the electrons from flying off into space. Since the protons in
the center are positively charged, the negatively charged electrons
are attracted to the center by the Coulomb force and orbit around the
center just like the planets orbiting a sun in a solar system due to the
attractive gravitational force.
 DIFFICULTIES WITH THE
RUTHERFORD MODEL
❑Atoms emit certain discrete characteristic frequencies
of electromagnetic radiation.
❑The Rutherford model is unable to explain this
phenomena.
❑Rutherford’s electrons are undergoing a centripetal
acceleration and so should radiate electromagnetic
waves of the same frequency.
❑The radius should steadily decrease as this radiation
is given off.
❑The electron should eventually spiral into the
nucleus, but it doesn’t.
EXERCISE 1
What was the main conclusion drawn from the Rutherford
gold foil experiment?
A) Electrons are located in fixed orbits around the nucleus.
B) The nucleus is composed of positively charged protons.
C) Atoms are mostly empty space, with a small, dense
nucleus.
D) Electrons are evenly distributed throughout the atom.
EXERCISE 1
What was the main conclusion drawn from the Rutherford gold
foil experiment?
A) Electrons are located in fixed orbits around the nucleus.
B) The nucleus is composed of positively charged protons.
C) Atoms are mostly empty space, with a small, dense nucleus.
D) Electrons are evenly distributed throughout the atom.
ANSWER : c
EXERCISE 2
Which particle was used by Rutherford in the gold
foil experiment to probe the structure of the
atom?
A) Protons
B) Electrons
C) Alpha particles
D) Neutrons
 EXERCISE 3
What unexpected observation did Ernest Rutherford make
during the gold foil experiment?
A) The electrons were evenly distributed throughout the
atom.
B) Some alpha particles were deflected at large angles.
C) The nucleus was composed of negatively charged
particles.
D) The nucleus was much smaller than originally thought.
EXERCISE 3
What unexpected observation did Ernest Rutherford make during the gold foil
experiment?

A) The electrons were evenly distributed throughout the atom.

B) Some alpha particles were deflected at large angles.
C) The nucleus was composed of negatively charged particles.
D) The nucleus was much smaller than originally thought.

ANSWER : B
 THE BOHR MODEL OF HYDROGEN ATOM
❑Improvement of quantum interpretation of Rutherford’s
Model.
❑It introduce the energy level of electron orbit using
quantum theory.
❑He suggests that electron moves about the nucleus in
circular orbits, but only certain orbit allow.
❑He applied the idea of Plank’s quantized energy level.
❑Bohr’s model explained the hydrogen’s spectral lines,
but failed to explain any other element’s lines.
❑For this and other reasons, the Bohr model was
replaced with a more sophisticated model called the
quantum-mechanical or wave-mechanical model.
THE BOHR MODEL OF HYDROGEN ATOM CONT.
❑Bohr proposed that the possible energy
states for atomic electrons were quantized –
only certain values were possible. Then the
spectrum could be explained as transitions
from one level to another.
❑What does the word “quantized” mean?
Bohr said that if an electron is quantized, it
means that the electron has a specific
amount of energy.
❑The word “quantum” means an “amount of
energy”.
 THE BOHR MODEL OF HYDROGEN ATOM CONT.
❑Each orbit was given a number, called the
quantum number.
❑Bohr orbits are like steps of a ladder, each at
a specific distance from the nucleus and each at
a specific energy.
❑Hydrogen’s single electron is in the n = 1 orbit
when it is in the ground state.
❑When energy is added, the electron moves to
the n = 2 orbit.
❑The electron releases energy as it falls back
towards the ground state.
BOHR’S POSTULATE
Bohr started with the
assumption that electron
moves in circular orbits
around the proton under the
influence of the Coulomb
force of attraction. The
Coulomb force produces the
centripetal acceleration.
BOHR’S POSTULATE CONT.
POSTULATE 1: Electron
can only exist and move in
certain allowed orbits
without radiating energy.
The total energy in
allowed orbit is constant.
BOHR’S POSTULATE CONT.
POSTULATE 2: The angular momentum of the
electron about the nucleus in allowed orbit is
quantized. It is an integer multiple of the plank’s
constant.
The circumference of the electron’s orbit must
contain an integral number of de Broglie
wavelengths.
2 r = n n = 1, 2, 3, ...
nh
Angular momentum, L = mvrn = n = n = 1,2,3.....
2
Where m : mass of electron
v : velocity of electron
r : radius of allowed orbit
 BOHR’S POSTULATE CONT.
POSTULATE 3: Electron can move or transit to
another energy level only when there is emission
or absorption of discrete energy. The transition
can be determined from the change in energy
of the energy level using the plank’s formula.

hc
Where E = E f − Ei = hf =

Ef : Energy of final stationary state
Ei : energy of initial stationary state
f : frequency of radiation
Ef<Ei corresponds to emission of energy
Ef>Ei corresponds to absorption of energy
EMISSION AND ABSORPTION LINE SPECTRUM
OF HYDROGEN GAS
WHY HYDROGEN?
❑Hydrogen is the simplest atom.
❑It has one electron in it’s structure.
❑It has a simple line spectrum.

❑The lines of different colours suggested that electrons travel at

orbits of fixed energy.
❑In other words, electrons orbit at a constant distance from the
nucleus, and they don’t move from that energy level unless they are
forced to move.
 EMISSION SPECTRUM OF HYDROGEN
When an electric current is passed
through a glass tube that contains
hydrogen gas at low pressure the
tube gives off blue light.
This light is passed through a prism
(as shown in the figure below), four
narrow bands of bright light are
observed against a black
background. We called this as
emission spectrum of hydrogen.
EMISSION SPECTRUM OF HYDROGEN CONT.
ABSORPTION LINE SPECTRUM OF HYDROGEN
GAS
EMISSION AND ABSORPTION LINE
SPECTRUM OF HYDROGEN GAS CONT.
Emission Absorption
The lines corresponds to The lines correspond to photons of
photons of discrete energies discrete energies that are absorbed
that are emitted when excited by the gases at the same
frequencies at which they emit
atomic states in the gas make light/photons.
a transition back to lower
energy levels. Dark line are observed. (missing
line)
EVIDENCE OF QUANTIZED ENERGY LEVEL: If an electron is excited to a
new energy level, it jumps to

LINE SPECTRUM OF VARIOUS GASES, that level instantaneously.

When it returns to a lower
level, it releases energy in a
quantized packet.
This release occurs in the
form of light of a specific
wavelength (colour).
Hence, atomic emission
spectra represent the
electrons returning to lower
energy levels.
Each packet of energy
corresponds to a line in the
atomic spectrum. There is
nothing between each line,
so the spectrum is
discontinuous.
QUALITATIVE STUDY OF FRANK AND HERTZ
EXPERIMENT
James Franck and Gustav Hertz performed an experiment which demonstrated
the existence of excited states in mercury atoms, helping to confirm the quantum
theory which predicted that electrons occupied only discrete, quantized energy
states.
 A contemporary Franck–Hertz tube is shown
Franck and Hertz's original experiment used in the photograph. It is fitted with three
a heated vacuum tube containing a drop of electrodes: an electron-emitting, hot cathode;
mercury; they reported a tube temperature a metal mesh grid; and an anode.
of 115 °C, at which the vapor pressure of
mercury is about 100 pascals (and far below The grid's voltage is positive relative to the
atmospheric pressure). cathode, so that electrons emitted from the
hot cathode are drawn to it.

The electric current measured in the

experiment is due to electrons that
pass through the grid and reach the
anode. The anode's electric potential
is slightly negative relative to the
grid, so that electrons that reach the
anode have at least a corresponding
amount of kinetic energy after
passing the grid.
QUALITATIVE STUDY OF FRANK AND HERTZ
EXPERIMENT
They discovered that, when an electron collided with a
mercury atom, it could lose only a specific quantity (4.9
electron volts) of its kinetic energy before flying away.
This energy loss corresponds to decelerating the
electron from a speed of about 1.3 million meters per
second to zero.
A faster electron does not decelerate completely after
a collision, but loses precisely the same amount of its
kinetic energy. Slower electrons merely bounce off
mercury atoms without losing any significant speed or
kinetic energy.
QUALITATIVE STUDY OF FRANK AND HERTZ
EXPERIMENT
EXERCISE 4
According to Bohr's postulates of the atomic model, which of the
following statements is true?
A) Electrons in an atom can occupy any energy level without restriction.
B) Electrons emit or absorb energy only when they transition between
different energy levels.
C) Electrons continuously spiral into the nucleus due to electromagnetic
radiation.
D) The position and momentum of an electron can be simultaneously
known with certainty.
EXERCISE 5
According to Bohr's atomic model, which of the following statements is
NOT a postulate?
A) Electrons revolve around the nucleus in fixed orbits without emitting
radiation.
B) Energy is emitted or absorbed by electrons only when they change from
one allowed orbit to another.
C) The angular momentum of an electron in an allowed orbit is quantized
and is given by L=nh/2π where n is an integer.
D) Electrons can exist in any orbit around the nucleus regardless of their
energy.
EXERCISE 6
In Bohr's atomic model, which of the following
quantities is quantized for an electron in a stable orbit?
A) Mass
B) Charge
C) Angular Momentum
D) Kinetic Energy
EXERCISE 7
In the Frank-Hertz experiment, when an electron
collides with a gas atom, what happens to the energy of
the electron?
A) The energy of the electron remains constant.
B) The energy of the electron decreases continuously.
C) The energy of the electron increases continuously.
D) The energy of the electron increases/decrease in
discrete steps.
RADIUS OF THE BOHR ORBIT
Mathematics of Bohr’s postulate and Results
Electron’s orbital angular momentum (From 2nd Postulate)
h
me vr = n n = 1, 2, 3, 
2
The total energy of the atom
E = KE + EPE
2
kZe
= 12 mv 2 −
r kZe 2
The energy of the atom can also be expressed as E=−
2r
RADIUS OF THE BOHR ORBIT

h
me vr = n n = 1, 2, 3, 
2

kZe 2
E=−
2r
DERIVATION OF BOHR RADIUS

Subs (1) in eq. (2)

 h2  n2
rn =  2 
2 
n = 1, 2, 3, 
 4 mke  Z
RADIUS OF THE BOHR ORBIT CONT.
The radii of the Bohr orbits are quantized.
 h2  n2
rn =  2 
2 
n = 1, 2, 3, 
 4 mke  Z
 This is based on the assumption that the electron can only exist in
certain allowed orbits determined by the integer n.
 Radii for Bohr orbits
(
rn = 5.29 10 m )
−11 n2
Z
n = 1, 2, 3, 

 When n = 1 and Z = 1, the orbit has the smallest radius, called the
Bohr radius, ao
 ao = 0.0529 nm
EXAMPLE 2
Calculate the Bohr radius for hydrogen atom
when electron at ground state, first excited state
and second excited state.
EXAMPLE 3
Which state in the hydrogen atom corresponds to
a radius of 0.8496 nm ?
EXAMPLE 4
An electron is in the second excited orbit of hydrogen,
corresponding to n = 3. Find
(a)radius of the orbit.
(b)the wavelength of electron in this orbit.
ENERGY OF QUANTUM STATE, N
OF THE HYDROGEN ATOM CONT.
QUANTUM STATE
-The quantum state is sometimes described
by a set of quantum numbers, n that pick out
the appropriate values for describing the
state.
-The integer n corresponding to the discrete
or quantized
-Different quantum states for a physical
system show discrete differences in the value
of the variables used to define the state.
ENERGY OF QUANTUM STATE, N OF THE
HYDROGEN ATOM CONT.

kZe 2
E=−
2r
DERIVATION OF BOHR ENERGY LEVEL

Subs (1) in eq. (2)

Subs radius,r in eq. (3)

 2 2 mk 2 e 4  Z 2
En = − 2
 2 n = 1, 2, 3, 
 h n
ENERGY OF QUANTUM STATE, N OF THE HYDROGEN ATOM
 2 2 mk 2 e 4  Z 2
En = − 2
 2 n = 1, 2, 3, 
 h n

( )
2
Z
En = − 2.18 10 −18 J 2 n = 1, 2, 3, 
n
Z2
En = −(13.6 eV ) 2 n = 1, 2, 3, 
n
Z: number of proton, For Hydrogen, Z =1

(1) 2
En = −(13.6 eV ) 2 n = 1, 2, 3, 
n
ENERGY LEVEL DIAGRAM FOR HYDROGEN
E3 = - (13.6 eV) 12 = - 1.51 eV Second excited state
32 energy

E2 = - (13.6 eV) 12 = - 3.40 eV First excited state

22 energy

E1 = lowest energy
E1 = - (13.6 eV) 12 = - 13.6 eV level ; n=1 ground
12 state
ELECTRON TRANSITION IN HYDROGEN
The Bohr model for an electron transition in hydrogen
between quantized energy levels with different
quantum numbers, n.

hf

hf
ENERGY OF QUANTUM STATE, N OF THE AN
ATOM
For different atoms, its has a different Z. By using the same
equation, subs the value of Z to get the Energy level at specific
quantum state.
Z2
En = −(13.6 eV ) 2 n = 1, 2, 3, 
n
The electron transition in an atom between quantized energy levels
with different quantum numbers, n. The equation is as below:
 1 1
E = E f − Ei = −(13.6 eV)Z  − 
2
n n 
 f i 
EXAMPLE 5
Show how to get the energy level as shown in figure. If Doubly-
ionized atom with Z = 3.
EXAMPLE 6
Calculate the energy of photon that emitted from hydrogen
atom if the transition of electron is from
a) n=4 to n =3
b) n = 5 to n =2
Which photon has the largest energy.
EXAMPLE 7
Calculate the changes in energy and determine if the
emission or absorption of light occur during the transition
of electron from :
A) n = 6 to n= 1
B) n= 1 to n = 4
C) n =3 to n = 5
Consider it’s a hydrogen atom.
EXAMPLE 8
Singly ionized helium, He+, a hydrogen-like system, has one
electron in the orbit corresponding to n = 1 when the atom
is in its ground state. Find
A)the energy of the system in the ground state in electron
volts, and
B) the radius of the ground-state orbit.
CONCEPT OF IONIZATION
Ionization is the process by which an atom or a molecule
acquires a negative or positive charge by gaining or losing
electrons.
The resulting electrically charged atom or molecule is called an
ion.
Ionization can result from the loss of an electron after
collisions with subatomic particles, collisions with other
atoms, molecules and ions, or through the interaction with
electromagnetic radiation.
CONCEPT OF IONIZATION CONT.
Notation for Degrees of Ionization

Chemist's
Suffix Ionization Examples
Notation

Not ionized
I H I, He I H, He
(neutral)
Singly
II H II, He II H+, He+
ionized
Doubly
III He III, O III He++, O++
ionized
IONIZATION ENERGY

Definition : The minimum energy needed to

remove an electron completely from an atom.
Formula for Ionization Energy, E
E = E∞ – Eground state/excited state
where E∞ = 0J
IONIZATION ENERGY - FACTORS AFFECTING THE
SIZE OF IONIZATION ENERGY

The more protons there The number of

The charge are in the nucleus, the The distance Attraction falls off very
more positively of the
rapidly with distance. electrons
on the charged the nucleus is,
and the more strongly electron from
An electron close to the
nucleus will be much between the
nucleus. electrons are attracted more strongly attracted outer electrons
to it. the nucleus. than one further away. and the nucleus.
CONCEPT OF EXCITATION
Definition : Transitions between the
orbits allowed by quantum
mechanics which is any quantum
state of the system that has a
higher energy than the ground state
cause by absorption of a photon
Excitation by absorption of light
(photon) and de-excitation by
emission of light (photon)
EXAMPLE 9
Li2+ is a lithium atom (Z=3) with only one electron.
Obtain the ionization energy of Li2+.