Chapter 4: Atomic Structure

Book: Modern Physics by Beiser (Chapters 4, 5 and 6)

Modern Physics by Kennethe S Krane
Modern Physics by Richtmyer
Evaluation:
NO Assignment
Mid-Semester : 40%
End-Semester : 60%
Atomic Structure
• The Nuclear Atom
An atom is largely empty space
• Electron Orbits
The planetary model of the atom and why it fails
• Atomic Spectra
Each element has a characteristic line spectrum
• The Bohr Atom
Electron waves in the atom
• Energy Levels and Spectra
A photon is emitted when an electron jumps from one energy level to a lower level
• Correspondence Principle
The greater the quantum number, the closer quantum physics approaches classical physics
• Nuclear Motion
The nuclear mass affects the wavelengths of spectral lines
• Atomic Excitation
How atoms absorb and emit energy
water fire earth air
1. All elements are composed of tiny
indivisible particles called atoms.
Atoms of the same element are identical.
2. Atoms of any one element are different
from those of any other element.
3. Atoms of different elements combine in
simple whole-number ratios to form chemical
compounds
4. In chemical reactions, atoms are combined,
separated, or rearranged – but never changed
into atoms of another element.
• Frederick Soddy (1877-1956) proposed the idea of isotopes in
1912
• Isotopes are atoms of the same element having different masses,
due to varying numbers of neutrons.
• Soddy won the Nobel Prize in Chemistry in 1921 for his work with
isotopes and radioactive materials.
water fire earth air
 Discovery of the Electron
In 1897, J.J. Thomson used a cathode ray tube to deduce the
presence of a negatively charged particle: the electron
 Discovery of electron: JJ Thomson (1897)
The experiment

Cathode rays are

negatively charged
particles

If ΔV (the voltage difference between the two deflection plates) = 0 there is no

deflection, but when ΔV is >> 0, there is Δx deflection towards the positive plate.
𝑞(−)
∆𝑥 − =
𝑚(−)
This negative particle from the cathode ray tubes was later
𝑞(+) named the electron and its mass was later determined to be
∆𝑥 + =
𝑚(+) very small (m = 9.11 x 10-31 kg).
∆𝑥 − 𝑞(−) 𝑞(+) 𝑚(+)
∆𝑥 +
= /
𝑚(−) 𝑚(+)
=
𝑚(−) Atoms are NOT indivisible!
m(-) <<< m(+)
 Conclusions from the Study of the Electron:

Cathode rays have identical properties regardless of the element

used to produce them. All elements must contain identically
charged electrons.

Atoms are neutral, so there must be positive particles in the atom to

balance the negative charge of the electrons.

Electrons have so little mass that atoms must contain other

particles that account for most of the mass.
 Thomson: “Plum Pudding” or “Chocolate Chip
Cookie” Model
• using available data on the atom, J.J. Thomson came up with the idea of having
charges embedded with Dalton’s Billiard Balls
• Also used cathode ray experiment to discover the existence of the electron

positive negative
(evenly distributed) “chocolate”
“dough”
part
Nuclear Model

• Ernest Rutherford discovered a huge flaw in the previous concept

of the atom during his now famous gold foil experiment
DISCOVERY OF THE NUCLEUS
Ernest Rutherford (Cambridge University, England, 1871-1937) studied α emission from
newly-discovered radioactive elements that he got from his friend Marie Curie.

Radium Bromide

Shipped to Rutherford
for experiment from
France to England
Ernest Rutherford
Marie Curie
(England)
(France)
Radium Bromide  particles

 Particles are He2+ ions - unknown in 1911

 Rutherford
• Discovered the Nucleus and the Positive
Protons
• Surmised atoms are made of mostly empty
space
• Didn’t know about the Neutrons
• Famous Gold Foil Experiment
 Rutherford’s problem:
In the following pictures, there is a target hidden by a cloud. To figure
out the shape of the target, we shot some beams into the cloud and
recorded where the beams came out. Can you figure out the shape of
the target?

Target Target
#1 #2
 The Answers:

Target #1 Target #2
 With postdocs Hans Geiger and undergraduate E. Marsden, the Rutherford Lab did the
experiment

Count rate = 132000 α

particles / min

Count rate = 132000 α particles / min with or without gold foil

Conclusion – Atom is mostly empty
Little advance experiment from the Rutherford Laboratory: Now the detector is all
around for detection of back scatter alpha particles

Mass of alpha particle: 8000 electron mass

Speed: 2X107 m/s

Count rate on backscatter side = 20 α

particles / min

Probability (P) of backscattering:

count rate backscattered 20
𝑃= =
count rate of incident particles 132000
= 2 × 10−4 (0.02%)
Rutherford said – “it was about as
incredible as if you had fired a 15 inch
shell at a piece of tissue paper and it
came back and hit you.”
Interpretation:
• The Gold atoms are mostly empty.
• A very tiny percentage of α particles hit something massive in the atom and backscatter
(bounce back). This observation indicates that most of the mass of the atom is concentrated
in a very small volume relative to the volume of the entire atom. → NUCLEUS.

Rutherford proposed the charge on the nucleus to be positive, since

electrons are negatively charged and atoms are neutral.

Charge of the electrons in an atom = - Ze

Z = atomic number
e = absolute value of electron’s charge
Charge of the nucleus of an atom = positive = +Ze

• Rutherford calculated the diameter of the nucleus to be 10-14 m.

His calculation related the probability of backscattering to the diameter of the nucleus based
on the size of the atom and the thickness of the foil.
Rutherford Scattering formula (Annexure of Chapter 4) → DERIVE IT AT HOME
The formula that Rutherford obtained for alpha particle scattering by a thin foil on the basis of
the nuclear model of the atom is

The predictions of Scattering Formula agreed with the measurements of Geiger and
Marsden, which supported the hypothesis of the nuclear atom.
Because N() is inversely proportional to
sin4(/2) the variation of N() with  is very
pronounced : only 0.14 percent of the incident
alpha particles are scattered.
 Nuclear Dimensions
Rutherford assumed that the size of a target nucleus is small compared with the minimum
distance R to which incident alpha particles approach the nucleus before being deflected away.
Rutherford scattering gives a way to find an upper limit to nuclear dimensions.
R = The distance of closest approach R for the most energetic alpha particles.
An alpha particle will have its smallest R when it approaches a nucleus head on, which will be
followed by a 180° scattering.
At the instant of closest approach the initial kinetic energy (KE) of the particle is entirely
converted to electric potential energy, and so at that instant
1 2𝑍𝑒 2
𝐾𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 𝑃𝐸 =
4𝜋𝜖0 𝑅
since the charge of the alpha particle is 2e and that of the nucleus is Ze.

1 2𝑍𝑒 2
Distance of closest approach 𝑅=
4𝜋𝜖0 𝐾𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙
The maximum KE found in alpha particles of natural origin is 7.7 MeV,
7.7 𝑀𝑒𝑉 = 1.2 × 10−12 𝐽
1
= 9 × 109 𝑁𝑚2 /𝐶 2
4𝜋𝜖0
1 2𝑍𝑒 2
𝑅=
4𝜋𝜖0 𝐾𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙
9 × 109 𝑁𝑚2 (2𝑍)(1.6 × 10−19 𝐶)2
=
𝐶2 1.2 × 10−12 𝐽
= 3.8 × 10−16 𝑍𝑚

The atomic number of gold is Z =79

𝑅 = 3.0 × 10−14 𝑚

The radius of the gold nucleus is therefore less than 3.0 × 10−14 𝑚, well under 10-4 the
radius of the atom as a whole.
Discovery of neutron 1. Chadwick placed polonium in a vacuum-sealed box,
which radiated alpha particles.
James Chadwick :- Rutherford’s
assistant

2. The alpha particles passed through a piece of

beryllium, causing the unknown radiation to accelerate
out.
3. Chadwick determined that the radiation was made
up of neutral particles, which he called neutrons. He
based this conclusion on the radiation's lack of
displacement by an electromagnet.
 ELECTRON ORBITS
Hydrogen atom : Single electron.
Assume a circular electron orbit for convenience
The centripetal force

holding the electron in an orbit r from the nucleus is provided by the electric force between them

The condition for a dynamically stable orbit is

Electron
velocity
 The total energy E of the electron in a hydrogen atom is the sum of its kinetic and
potential energies, which are

The minus sign → PE = 0 at 𝑟 = ∞ , that is, when

the electron and proton are infinitely far apart

Total energy of hydrogen atom

The total energy of the electron is negative. This holds for every atomic electron and reflects
the fact that it is bound to the nucleus. If E were greater than zero, an electron would not
follow a closed orbit around the nucleus.
 (FAILURE OF) THE CLASSICAL DESCRIPTION OF AN ATOM
How is an electron bound to the nucleus? What is the force between them? Coulomb’s Force Law
describes the force of attraction and repulsion between charged particles.

When charges are the same sign, acceleration of the particles will push them apart. The
force is positive and repulsive.

When charges are the opposite sign, acceleration will pull them together. The force is
negative and attractive.

If the electron and the nucleus are infinitely attracted, why do

Consider an H atom (Z=1) with 1 electron and 1 proton.
they stay apart.
When r → ∞, F(r) = 0
Coulomb’s law only describes force as a function of r
As r → 0, F(r) = ∞ → infinitely attractive (distance). It doesn’t tell us how r changes with time, t.
To write the force as a function of time, we need a classical equation of motion that can
describe how the electron and nucleus move under force.

Newton’s Second law:

Force, F = ma (mass X acceleration)

F= m (dv/dt) (function of velocity) = m(d2r/dt2) (function of distance)

Plug in Coulomb’s force law

For rinitial= 0.5X10-10m, calculate how fast it should go to zero.

The answer is very fast.

r=0 at t = 10-10 s

This predicts that the electron should crash into the nucleus in 10-10 sec. But
why is it not doing that?
 So what is the problem here?

1. Coulomb force law?

2. Newton’s second law?

So problem here is → The laws of classical Mechanics no longer work at this size scale.

A new kind of mechanics was needed to describe this and other “unsettling”
observations.

QUANTUM MECHANICS provides a single and comprehensive theory that

explains the behavior of matter on an atomic (nanometer or smaller) scale.
Early quantum ideas and the Bohr Model
Bohr’s postulates were based on the observation of discrete spectra and the results of the -
scattering experiment of Rutherford.
The postulates were
▪ Electrons move around the nucleus in discrete orbits. These orbits correspond to fixed
energies and are stable (i.e. no radiation is emitted by such electrons)
▪ Radiation is emitted only when the electron jumps from one discrete orbit to another orbit
of a lower energy. When electrons absorb radiation, the reverse transition occurs.
▪ A dynamic equilibrium exists between the centrifugal force and the coulomb force
between the electron and the nucleus:

𝑍(𝑒)2 𝑚𝑣 2 𝑍𝑒 2
2
= →𝑣=
4𝜋𝜖𝑜 𝑟 𝑟 4𝜋𝜖𝑜 𝑚𝑟

The electron revolves at the frequency  in the orbit. Classical electrodynamics predicts that
the charge will radiate at this very frequency and lose energy. Bohr’s postulates override this.
 For H-atom the total energy of the electron is

1 𝑒 2 𝑍𝑒 2
𝐸 = 𝐸𝑘𝑖𝑛 + 𝐸𝑝𝑜𝑡 = 𝑚𝑣 2 − 𝑣=
2 4𝜋𝜖𝑜 𝑟 4𝜋𝜖𝑜 𝑚𝑟

𝑒2
Total Energy, 𝐸 = −
8𝜋𝜖𝑜 𝑟

Bohr’s important insight was to recognize that the frequency of radiation

(according to the postulates) should be given by

ℎν = 𝐸𝑛 − 𝐸𝑛′

where h is the radiation quantum as proposed by Planck and this radiation must
be the same as that.
 Atomic Spectra
Each element has a characteristic line spectrum
Spectral Series
The quantity R, known as the Rydberg constant, has the value

H line → n = 3,
H line → n = 4, and so on.
4
The series limit corresponds to 𝑛 = ∞, at  = , in agreement with experiment.
𝑅

Balmer series → wavelengths in the visible region of the hydrogen spectrum.

Lyman series → wavelengths in the ultraviolet region
Three spectral series have been found in the infrared region.
The wavelengths specified by the formulas

The value of R is the same in all the spectral series.

Rydberg-Ritz Combination Principle
There are pair of spectral lines with the property that the sum of their wave numbers is
also a wave number of a spectral line of the same atom.
A similar relation also holds for the difference of the wave numbers of some pairs of
spectral lines.
Transition from mth to nth level
ℎ𝑣𝑚𝑛 = 𝐸𝑚 − 𝐸𝑛
m

Transition from nth to pth level

n ℎ𝑣𝑛𝑝 = 𝐸𝑛 − 𝐸𝑝

Transition from mth to pth level

p ℎ𝑣𝑚𝑛 + ℎ𝑣𝑛𝑝 = 𝐸𝑚 − 𝐸𝑛 + 𝐸𝑛 − 𝐸𝑝 = 𝐸𝑚 − 𝐸𝑝 = ℎ𝑣𝑚𝑝
 THE BOHR ATOM – Understanding Stability
The de Broglie wavelength of an electron is

𝑣 = electron velocity

Radius of electron orbit, r = 5.3 × 10−11 𝑚

The electron wavelength

This wavelength is exactly the same as the circumference of the electron orbit,
What makes Bohr’s allowed energy levels allowed?

Recall what happens when we force

waves into confined spaces:
Confined waves

Only waves with wavelengths that just fit in survive

(all others cancel themselves out)
Electrons in atoms are confined matter waves

This wave, as it goes around, will interfere

with itself destructively and cancel itself out

Bohr’s allowed energy states correspond to those

with orbits that are integer numbers of wavelengths
Electrons in atoms are confined matter waves
However, if the circumference is exactly an integer number
of wavelengths, successive turns will interfere constructively

Bohr’s allowed energy states correspond to those

with orbits that are integer numbers of wavelengths
Bohr orbits
 An electron can circle a nucleus only if its orbit contains an integral
Bohr orbits number of de Broglie wavelengths
 rn = the radius of the orbit that contain n
wavelengths.
n = the quantum number of the orbit.
Substitute , the electron wavelength

The possible electron orbits are those

whose radii

The innermost radius is called Bohr Radius

The other radii in terms of Bohr Radius are

ENERGY LEVELS AND SPECTRA
The electron energy En is given in terms of the orbit
radius rn as
𝑒2
𝐸𝑛 = −
8𝜋𝜖0 𝑟𝑛

𝑛2 ℎ2 𝜖0
𝑟𝑛 = 𝑛 = 1, 2, 3 … .
𝜋𝑚𝑒 2

The energy levels of the hydrogen atom

𝑚𝑒 4 1 𝐸1
𝐸𝑛 = − 2 2 2 = 2 𝑛 = 1, 2, 3 … .
8𝜖0 ℎ 𝑛 𝑛
𝐸1 = −2.18 × 10−18 𝐽 = −13.6𝑒𝑉

Rydberg constant
 𝐸1 𝐸1 1 1
Origin of line spectra ∆𝐸 = 𝐸𝑓 − 𝐸𝑖 = 2 − 2 = 𝐸1 2 − 2
𝑛𝑓 𝑛𝑖 𝑛𝑓 𝑛𝑖

𝐸1 = −2.18 × 10−18 𝐽 = −13.6𝑒𝑉 = −Rydberg constant

 CORRESPONDENCE PRINCIPLE The greater the Q#, the closer Quantum Physics
approaches classical mechanics.
According to electromagnetic theory, an electron moving in a circular orbit radiates EM waves whose frequencies
are equal to its frequency of revolution and to harmonics (that is, integral multiples) of that frequency. In a
hydrogen atom the electron’s speed is

frequency of revolution f of the electron is

The radius rn of a stable orbit is given in terms of its quantum number n

𝑚𝑍 2 𝑒 4 1 2
13.6𝑒𝑉
𝐸𝑛 = − 2 2 = −𝑍
8𝜖0 ℎ 𝑛2 𝑛2
Under what circumstances should the Bohr atom behave classically?
If the electron orbit is so large that we might be able to measure it directly, quantum effects ought not to dominate.
Example → An orbit 0.01 mm across, for instance, meets this specification, its quantum number is n =435. (example
4.3 of your text book)
𝑟𝑛
n=
What does the Bohr theory predict such an atom will radiate? 𝑎0
A hydrogen atom: nith energy level → nfth energy level : emits a photon whose frequency is

n for the initial quantum number ni

n − p (where p=1, 2, 3, . . .) : for the final quantum number nf.

When ni and nf are both very large, n >> p, and

When p=1, the frequency of the radiation is exactly the same as the frequency of revolution f of the orbital electron

𝐸1 2 𝐸1 2𝑝
𝑓=− 𝑣=−
ℎ 𝑛3 ℎ 𝑛3
Multiples of this frequency are radiated when p=2, 3, 4, .

Quantum and Classical pictures of the hydrogen atom make the same predictions in the limit of very large quantum numbers.

When n=2, a radiation frequency that differs by almost 300 percent.

When n = 10,000, the discrepancy is only about 0.01 percent.

The requirement that quantum physics give the same results as classical physics in the limit of large quantum numbers
was called by Bohr the correspondence principle.
 NUCLEAR MOTION
The nuclear mass affects the wavelengths of spectral lines

• Assumption: The hydrogen nucleus (a proton) remains

stationary while the electron orbits it.
• In reality, both the nucleus and electron orbit their common
center of mass, which lies near the nucleus due to its much
greater mass.
• This system is equivalent to a single particle of mass m’ orbiting
the heavier nucleus.

m = electron mass
M = nuclear mass

• To account for the nucleus's motion in a hydrogen atom, we replace the electron with a particle of mass m’. The
atom's energy levels then become

𝑚𝑒 1′ 4
𝑚 ′
𝐸1 𝑚𝑒 4 1 𝐸1
𝐸′𝑛 = − 2 2 2 = − 2 2 2 = 2
8𝜖0 ℎ 𝑛 𝑚 𝑛2 8𝜖0 ℎ 𝑛 𝑛
 Due to the nucleus's motion, all hydrogen energy levels shift by the fraction

This represents an increase of 0.055 percent because the energies En, being smaller in absolute value, are therefore
less negative.

• The energy equation removes the discrepancy between the predicted wavelengths of the spectral lines of
hydrogen and the measured ones.
• The value of the Rydberg constant R without correcting for nuclear motion is 1.0973731 X 107m-1;
• The correction lowers R to 1.0967758 X 107 m-1.
• The notion of reduced mass played an important part in the discovery of deuterium,
Deuterium nucleus contains a neutron as well as a proton.

• Because of the greater nuclear mass, the spectral lines of deuterium are all shifted slightly
to wavelengths shorter than the corresponding ones of ordinary hydrogen.

• H line of deuterium → Transition n = 3 → n = 2 energy level → Wavelength 656.1 nm.

• H line of Hydrogen → Transition n = 3 → n = 2 energy level → Wavelength 656.3 nm.

• Identification of deuterium in 1932 by the American chemist Harold Urey.

 ATOMIC EXCITATION
How atoms absorb and emit energy

• Auroras are caused by streams of fast protons and electrons from the sun
that excite atoms in the upper atmosphere.
• The green hues of an auroral display come from oxygen
• The reds originate in both oxygen and nitrogen.
Franck-Hertz Experiment
Accelerating
Grid Collector
• The Filament ejects electrons in
Hg
e- Hg the gas filled tube.
• A variable (positive) accelerating
Electrometer
voltage, VA, is applied to the grid.
6V
VA Vr • The electron acquire kinetic
Filament energy K=eVA
Supply
1.5 V
0-40 V
Retarding
Accelerating
voltage
voltage

• There is (negative) retarding voltage (Vr) between the grid and collector.
• Only electrons having enough energy will overcome this potential and reach
the collector and contribute to current measured with an Electrometer.
 Accelerating
Grid Collector

Hg
e- Hg

Electrometer
VA Vr
6V
Filament
Supply
1.5 V
0-40 V
Retarding
Accelerating
voltage
voltage

• If Vr > VA → no electron can reach the collector, so no current would be measured.

• If Vr < VA → if the tube is highly evacuated, most of the electrons would reach the
collector and have energy |e|(VA-Vr)
 Accelerating
Grid Collector

Hg
e- Hg

Electrometer
VA Vr
6V
Filament
Supply
1.5 V
0-40 V
Retarding
Accelerating
voltage
voltage

• If the tube contains some gas, the electrons can loose energy via collisions with the gas
atoms.
- Such collisions are inelastic, i.e. electrons lose energy, which is transferred to internal
energy of atoms in the gas.
• Thus, even in the case when Vr < VA , it is possible that the electrons would not be able to
reach collector, and won’t contribute to the current.
• Franck and Hertz observed the collector current as a function of VA (>Vr) when tube was
filled with various gases (result for mercury gas is shown here)
• At first, the current increased as was expected for a typical vacuum tubes, but as ~4.9V
current suddenly dropped.
• Then, the increase resumed until 9.8 V, and so on.
• The current drops because fewer electrons
reach the collector.

• This occurs only if the electrons undergo

elastic collisions.

• Thus, when VA=4.9 X n Volts (n=1, 2, 3,

….) the electrons undergo inelastic
collisions with Hg atoms.

• In inelastic collision kinetic energy of

electrons is transferred to the internal
energy of Hg atoms- Hg atoms absorb the
energy of electrons.
Why do we see the drop only at specific voltages?

→If distribution of energy levels of Hg atoms is continuous, then KE should be

transferred to Hg atoms regardless of the energy of electrons.

→However, if we assume that Hg energy levels are discrete, then only when
electrons reach certain energy they undergo inelastic collision with Hg atoms.

→ Thus energy spectrum of Hg atom is such that an electron energy level lies ~4.9
eV above the ground state.
Why did Franck and Hertz not observe dips
in the current at other voltage?

→Their experiment was not sufficiently sensitive.

→Since as soon as electrons gain energy of 4.9eV

they transfer it to the Hg atoms, only small
fraction of the electrons could have higher
energies (e.g 6.65eV), making it difficult to
observe current dips associated with other
(higher) voltages.
Chapter 4 Ends
Basic Concepts of Quantum Mechanics
Classical (Newtonian) mechanics is inaccurate when applied to the systems
with atomic dimensions.
Quantum mechanics is necessary background knowledge for understanding
electrons in atoms.
 The Bohr Model of the Atom

• The H-atom emission spectrum was rationalized by Bohr (1913):

– Energies of H atom are restricted to certain discrete values
(i.e. electron is restricted to well-defined circular orbits, labelled by
quantum number n).
– Energy (light) absorbed in discrete amounts (quanta = photons),
corresponding to differences between these restricted values:
E = E2 − E1 = h
e−
n2 E2 E2
h h
n1
p+ E1 E1
Absorption Emission

Conclusion: Spectroscopy provides direct evidence for quantization of

energies (electronic, vibrational, rotational etc.) of atoms and molecules
Limitations of Bohr Model & Rydberg-Ritz Equation
• The model only works for hydrogen (and other one electron ions)
– ignores e-e repulsion.

• Does not explain fine structure of spectral lines.

• Note: The Bohr model (assuming circular electron orbits) is fund

amentally incorrect.
Wave-Particle Duality
Light: wave nature (diffraction, refraction, interference….)
particle nature (photoelectric effect, Compton effect)
called “photon”
Electron: particle nature (m0, q ….)
wave nature (diffraction, refraction, interference…)

de Broglie’s matter wave: All particles have the properties of wave.

ℎ ℎ de Broglie’s
λ= p=
𝑚ʋ λ hypothesis

Low dimensional materials (2D, 1D) in terms of electrical

properties: size of reduced dimensions approaches λ of electron
 Wavefunctions
• A particle trajectory is a classical concept.
• In Quantum Mechanics, a “particle” (e.g. an electron) does not
follow a definite trajectory {r(t),p(t)}, but rather it is best
described as being distributed through space like a wave.

Definitions
• Wavefunction () – a wave representing the spatial distribution
of a “particle”.
• e.g. electrons in an atom are described by a wavefunction
centred on the nucleus.
•  is a function of the coordinates defining the position of the
classical particle:
– 1-D (x)
– 3-D (x,y,z) = (r) = (r,,) (e.g. atoms)
•  may be time dependent – e.g. (x,y,z,t)
The Importance of 
•  completely defines the system (e.g. electron in an atom
or molecule).
• If  is known, we can determine any observable property
(e.g. energy, vibrational frequencies, …) of the system.
• QM provides the tools to determine  computationally, to
interpret  and to use  to determine properties of the
system.
To get full knowledge of a problem POSITION and MOMENTUM
need to be known

ℏ
For QUANTUM particles its Uncertain → ∆𝑥∆𝑝𝑥 ≥
2

First Postulate Introduce a parameter called

Ψ(𝑥)

How to obtain? (We are yet to see!)

∆𝑥 and ∆𝑝𝑥 are not absolute values → they represents the
accuracy of measurement
Quantum Mechanics says → The state of a Quantum Object is
completely specified by a wavefunction Ψ 𝑥 .

Does it mean something?

Probability
Ψ ∗ 𝑥 Ψ 𝑥 is the probability density.
For Quantum Particles probability gives full information.
Probability that the particle can be found in the interval dx

Ψ ∗ 𝑥 Ψ 𝑥 𝑑𝑥

A given wavefunction of the form Ψ 𝑥 = 𝐴𝑓(𝑥) needs to get

normalized such that total Probability =1, using the condition for
NORMALIZATION

න Ψ ∗ 𝑥 Ψ 𝑥 𝑑𝑥 = 1
𝑎𝑙𝑙

Suitable A is obtained

Probability must be real and positive

(0  P  1).
Quantum Mechanics says → The wavefunction Ψ 𝑥 has to be
single valued
 Linearity and Superposition

Let Ψ𝟏 (𝒙) and Ψ𝟐 (𝒙) represent the two wave functions of a

quantum system, then the linear superposition will also be
a valid wavefunction for the same quantum system.

Ψ 𝑥 = 𝑎1 Ψ𝟏 (𝒙)+ 𝑎2 Ψ𝟐 (𝒙)
Demonstration of superposition
 Expectation value

Let Ψ 𝑥 describe the wavefunction of a quantum system,

average value of the position (x) is given by the expectation
value integral:

𝑥 = න Ψ ∗ 𝑥 𝑥Ψ 𝑥 𝑑𝑥
Expectation or average: no of students v/s height
Expectation or average position

𝑃1 𝑥1 + 𝑃2 𝑥2
𝑥 =
𝑃1 +𝑃2
 Expectation value of position of a quantum particle

Probability that the particle can be found in the interval dx

Ψ ∗ 𝑥 Ψ 𝑥 𝑑𝑥

What is the expectation value of the position of the particle ?

𝑃1 𝑥1 + 𝑃2 𝑥2 ‫𝑥 𝑙𝑙𝑎׬‬Ψ ∗ 𝑥 Ψ 𝑥 𝑑𝑥
𝑥 = 𝑥 =
𝑃1 + 𝑃2 ‫ 𝑙𝑙𝑎׬‬Ψ ∗ 𝑥 Ψ 𝑥 𝑑𝑥
One-electron Schrödinger equation
General Formulation

(1)There exist a wavefunction, Ψ(x, y, z, t), describing the dynamic

behavior of the system. mathematically complex
quantity

(2) Ψ and 𝛻Ψ must be continuous, finite, and single-valued for all

values of x, y, z, and t.

∗
(3) Ψ ΨdV = Ψ 2 dV : the probability that the particle will be
found in the spatial volume element dV.
∗
න Ψ ΨdV = 1: normalization
 Wave Mechanics
• The wavefunction () contains all the information we need
to know about any particular system.
• How do we determine  and use it to deduce properties of
the system?

Operators and Observables

• If  is the wavefunction representing a system, we can

write:
෡ ψ = Qψ
𝐐

where Q – “observable” property of system (e.g. energy,

momentum, dipole moment …)
෡ – operator corresponding to observable Q.
𝐐
• This is an eigenvalue equation and can be rewritten
as:
෡ ψ =Q×ψ
𝐐

operator Q acting on function  multiplied

function  by a number Q
(eigenfunction) (eigenvalue)

(Note:  can’t be cancelled).

Examples: d/dx (eax) = a eax

d2/dx2 (sin ax) = −a2 sin ax

Quantization of the Wavefunction Not continuous
The Born interpretation of  places restrictions on
the form of the wavefunction: Slope discontinuous
(a)  must be continuous (no breaks);

(b) The gradient of  (d/dx) must be continuous

(no kinks); Not single valued

(c)  must have a single value at any point in space;

(d)  must be finite everywhere; Infinite over a finite

region
(e)  cannot be zero everywhere.

• Other restrictions (boundary conditions) depend on the exact system.

• These restrictions on  mean that only certain wavefunctions and  only certain
energies of the system are allowed.
 Quantization of   Quantization of E
To find  and calculate the properties (observables) of a system:
෡
1. Construct relevant operator 𝐐
2. Set up equation ෡ ψ = Qψ
𝐐
3. Solve equation  allowed values of  and Q.
Quantum Mechanical Position and Momentum Operators

1. Operator for position in the x-direction is just multiplication by x

𝐱ො ψ = xψ
ℏ d
2. Operator for linear momentum in the x-direction: ෝ𝐱 =
𝐩
𝑖 dx
ℏ dψ
ෝ 𝐱 ψ = px ψ 
𝐩 ⋅ = px ψ
𝑖 dx

(solve first order differential equation   , px).

Simple examples of operator
Constructing Kinetic and Potential Energy QM Operators
1. Write down classical expression in terms of position and momentum.
2. Introduce QM operators for position and momentum.

Examples ℏ d
෡𝐱 ෝ𝐱 =
𝐩
1. Kinetic Energy Operator in 1-D 𝐓 𝑖 dx

px 2 ෝ𝐱2
𝐩 ℏ2 d 2
CM Tx =  QM ෡𝐱 =
𝐓 =−
2m 2m 2m dx 2
2. KE Operator in 3-D ෡
𝐓
“del-squared”
CM QM
p2 px 2 + py 2 + pz 2 ෝ2
𝐩 ℏ2 𝜕 2 𝜕2 𝜕2 ℏ2 2
T= = ෡=
𝐓 =− + + =− ∇
2m 2m 2m 2m 𝜕x 2 𝜕y 2 𝜕z 2 2m
partial derivatives
operate on (x,y,z)
෡ (a function of position)
3. Potential Energy Operator 𝐕
 PE operator corresponds to multiplication by V(x), V(x,y,z) etc.
The Schrödinger Equation (1926)
• The central equation in Quantum Mechanics.
• Observable = total energy of system.

Schrödinger Equation ෡ ψ = Eψ
𝐇 ෡ Hamiltonian Operator
𝐇
E Total Energy
෡ =𝐓
where 𝐇 ෡+𝐕
෡ and E = T + V.

• SE can be set up for any physical system.

෡ depends on the system.
• The form of 𝐇
• Solve SE   and corresponding E.
Examples

1. Particle Moving in 1-D (x)

ℏ2 𝜕 2 ψ
෡ψ = 𝐓
𝐇 ෡ψ + 𝐕
෡ψ = Eψ − 2
+ V x ψ = Eψ
2m 𝜕x

• The form of V(x) depends on the physical situation:

– Finite well V(x) = 0 for all a range of x and
finite for rest.
– Infinite well V(x) = 0 for all a range of x and
infinite for rest.
– Harmonic oscillator V(x) = ½kx2
The Particle in A Box
 Particle in 1-dimensional box
Time Independent Schrödinger Equation
• Infinite walls −ℏ2 𝑑 2 𝜓(𝑥)
+ 𝑉(𝑥)𝜓 = 𝐸𝜓
2𝑚 𝑑𝑥 2
PE TE
Region I Region II Region III KE

V(x)=∞ V(x)=0 V(x)=∞ System

Particle of mass m in 1-D box of
0 L x length L.
Position x = 0→L.
Particle cannot escape from box as PE V(x)=  for x = 0, L (walls).
PE inside box: V(x)= 0 for 0< x < L.
Restrictions on 

• In principle Schrödinger Eqn. has an infinite number of solutions.

• So far we have general solutions: any value of {,E}.

• BUT – due to the Born interpretation of , only certain values of

 are physically acceptable:
– outside box (x<0, x>L) V =   impossible for particle to be outside the
box
 2 = 0   = 0 outside box.
–  must be a continuous function
 Boundary Conditions  = 0 at x = 0
 = 0 at x = L.
Applying boundary conditions: Restrictions on 

Region I Region II Region III

V(x)=∞ V(x)=0 V(x)=∞

0 L x

Region I and III:

−ℏ2 𝑑2 𝜓(𝑥)
2
+ ∞ ∗ 𝜓 = 𝐸𝜓
2𝑚 𝑑𝑥

=> 𝜓 2 =0
 Region II:

𝑑 2 Ψ(𝑥) 2𝑚𝐸 Second derivative of a function equals a negative

2
= − 2 Ψ(𝑥) constant times the same function.
𝑑𝑥 ℏ
Functions with this property sin and cos.

𝑑 2 sin( 𝑎𝑥) 2 sin( 𝑎𝑥)

= −𝑎
𝑑𝑥 2
𝑑 2 cos( 𝑎𝑥) 2 cos( 𝑎𝑥)
= −𝑎
𝑑𝑥2

Region I Region II Region III

V(x)=∞ V(x)=0 V(x)=∞

0 L x
 Region II: b) x=L ψ=0
−ℏ2 𝑑 2 𝜓(𝑥) 0 = 𝐴 sin 𝑘 𝐿
2
= 𝐸𝜓
2𝑚 𝑑𝑥
𝐵𝑢𝑡𝐴 ≠ 0
𝑑 2 𝜓(𝑥) 2𝑚
=> − = 2 𝐸𝜓 𝑘𝐿 = 𝑛𝜋
𝑑𝑥 2 ℏ
This is similar to the general differential Thus, wave function:
equation: 2𝑚𝐸 𝑛𝜋𝑥
𝑘2 = 𝜓𝐼𝐼 = 𝐴 sin
𝑑 2 𝜓(𝑥) ℏ2 𝐿
2
− 2
= 𝑘 𝜓
𝑑𝑥 But what is ‘A’?
𝜓 = 𝐴 sin 𝑘 𝑥 + 𝐵 cos 𝑘 𝑥

Applying boundary conditions:

a) x=0 ψ=0
Region I Region II Region III
0 = 𝐴 sin 0 𝑘 + 𝐵 cos 0 𝑘
V(x)=∞ V(x)=0 V(x)=∞
0=0+𝐵∗1
=> 𝐵 = 0
0 L x
 Normalizing wave function:
𝐿 𝐿
1 𝑐𝑜𝑠2𝑘𝑥
න(𝐴 sin 𝑘 𝑥)2 𝑑𝑥 =1 න 𝐴2 ( − ) 𝑑𝑥 = 1
2 2
0 0

𝐿
𝑛𝜋
𝑥 sin 2 𝑘𝑥 𝑘=
𝐴 2 − ቤ =1 𝐿
2 4𝑘 0

𝑛𝜋
2
𝐿 sin 2 𝐿 𝐿
𝐴 − 𝑛𝜋 =1
2 4
𝐿

2
𝐿
𝐴 =1
2

2
𝐴 =
𝐿
Thus normalized wave function is:
2 𝑛𝜋𝑥
𝜓𝐼𝐼 = sin
𝐿 𝐿
Calculating Energy Levels:

2
2𝑚𝐸
𝑘 = 2
ℏ
𝑘 2 ℏ2 𝑛𝜋
𝐸= 𝑘=
2𝑚 𝐿
𝑘 2 ℎ2
𝐸= ℎ
2𝑚4𝜋 2 (ℏ = )
2𝜋
𝑛2 𝜋 2 ℎ2
𝐸= 2
𝐿 2𝑚4𝜋 2

Thus Allowed Energies, En, are:

𝑛2 ℎ2
𝐸𝑛 =
8𝑚𝐿2
Quantum Numbers

• There is a discrete energy state (En),

corresponding to a discrete
wavefunction (n), for each integer
value of n.

• Quantization – occurs due to boundary

conditions and requirement for  to be
physically reasonable (Born
interpretation).

• n is a Quantum Number – labels each

allowed state (n) of the system and
determines its energy (En).

• Knowing n, we can calculate n and En.

 Particle in a 1-Dimensional Box
2 𝑛𝜋𝑥 2 𝑛2 ℎ2
2 𝑛𝜋𝑥 𝜓𝐼𝐼 2 = sin 𝐸𝑛 =
𝜓𝐼𝐼 = sin 𝐿 𝐿 8𝑚𝐿2
𝐿 𝐿
1) Difference b/w adjacent
energy levels:

2) Non-zero zero point energy

+ + 3) Probability density is structured

+ with regions of space demonstr
- ating enhanced probability.

+ +

E  
Properties of the Wavefunction

2 n𝜋x
• Wavefunctions are standing waves: ψn = sin
L L

• The first 5 normalized wavefunctions for the particle in the 1-D

box:

• Successive functions possess one more half-wave ( they

have a shorter wavelength).

• Nodes in the wavefunction – points at which n = 0 (excluding

the ends which are constrained to be zero).

• Number of nodes = (n-1) 1 → 0; 2 → 1; 3 → 2 …

Curvature of the Wavefunction

• If y = f(x) dy/dx = gradient of y (with respect to x).

d2y/dx2 = curvature of y.
𝜕2ψ
T∝ +. . . . .
• In QM Kinetic Energy  curvature of  𝜕x 2

• Higher curvature  (shorter )  higher KE

• For the particle in the 1-D box (V=0):

𝜕 2 ψn n2
KE En = Tn ∝ 2
∝ 2
𝜕x L
 n2 ℎ 2
Energies En =
8mL2

• En  n2/L2  En as n (more nodes in n)

En as L (shorter box)
n (or L)  curvature of n
 KE  En

E 2 node
E

L
1

L1 L2
• En  n2  energy levels get further apart as n
n E
9ℎ2
3 E3 =
8mL2

4ℎ2
2 E2 =
8mL2

ℎ2 ℎ2
1 E1 = ZPE =
8mL2 8mL2
0

• Zero-Point Energy (ZPE) – lowest energy of particle in box:

ℎ2
ZPE = Emin = E1 =
8mL2

• CM Emin = 0
• QM E = 0 corresponds to  = 0 everywhere (forbidden).
• If V(x) = V  0, everywhere in box, all energies are
shifted by V.

V=0 V0
E2=E2+V
n2 ℎ 2
En = 2
+V E2
8mL
E1=E1+V
V
E1
Density Distribution of the Particle in the 1-D Box

• The probability of finding the particle

between x and x+dx (in the state 
represented by n) is:
Pn(x) = n(x)2 dx = (n(x))2 dx (n is real)

2 2 n𝜋x
 Pn x = L sin dx
L 2

• Note: probability is not uniform

– n2 = 0 at walls (x = 0, L) for all n.
– n2 = 0 at nodes (where n = 0). 2
Expectation value of position and its
uncertainty
 Expectation values Position
𝐿
2 2
𝑛𝜋𝑥
𝑥 = න 𝑥 𝑠𝑖𝑛 𝑑𝑥
0 𝐿 𝐿
2 𝐿 1 1 2𝑛𝜋𝑥
= න 𝑥( − cos ) 𝑑𝑥
𝐿 0 2 2 𝐿
2𝑛𝜋𝑥 2𝑛𝜋𝑥 𝐿
2 𝑥2 sin cos
𝐿 𝐿
= −𝑥 −
𝐿 4 4𝑛𝜋 𝑛𝜋 2
𝐿 8
𝐿 0
𝐿 𝐿
2 𝑥2 2 𝐿2 2𝜋𝑛𝑥 2𝑛𝜋𝑥 2𝑛𝜋𝑥
= − sin + cos
𝐿 4 0 𝐿 8𝑛2 𝜋 2 𝐿 𝐿 𝐿 0

Since sin(n) = 0 and cos(n)=1, for all the values of n the expectation
value of x is
2 𝐿2 𝐿
𝑥 = =
𝐿 4 2
 2 𝐿 2 2 𝑛𝜋𝑥
𝑥2 = න 𝑥 𝑠𝑖𝑛 𝑑𝑥
𝐿 0 𝐿

2 𝐿 2 1 1 2𝑛𝜋𝑥
𝑥2 = න 𝑥 ( − cos ) 𝑑𝑥
𝐿 0 2 2 𝐿

2𝑛 2𝜋 2 − 3
𝑥2 = 𝐿2
6𝑛2 𝜋 2

Extra – Not part of Syllabus

Uncertainity

(∆𝑥)2 = 𝑥 2 − 𝑥 2

2 2 2
2𝑛 𝜋 − 3 𝐿
= 𝐿2 2 2
−
6𝑛 𝜋 4
2 2
2
𝑛 𝜋 −6
=𝐿
12𝑛2 𝜋 2

Extra – Not part of Syllabus

Expectation value of Momentum

And square of momentum

 Momentum

1
𝐿 1/2
2 2 𝑛𝜋𝑥 𝑖ℎ 𝑑 2 𝑛𝜋𝑥
𝑝𝑥 = න 𝑠𝑖𝑛 − 𝑠𝑖𝑛 𝑑𝑥
0 𝐿 𝐿 2𝜋 𝑑𝑥 𝐿 𝐿

2𝜋𝑖𝑛ℏ 𝐿 𝑛𝜋𝑥 𝑛𝜋𝑥

𝑝𝑥 = − 2 න 𝑠𝑖𝑛 𝑐𝑜𝑠 𝑑𝑥 = 0
𝐿 0 𝐿 𝐿

odd even

Also try with

𝑛𝜋𝑥
𝑠𝑖𝑛 =u
𝐿

𝑛𝜋 𝑛𝜋𝑥
𝑐𝑜𝑠 dx = du
𝐿 𝐿
𝐿 𝑛𝜋𝑥 𝑛𝜋𝑥 𝐿 𝑛𝜋𝑥
‫׬‬0 𝑠𝑖𝑛 𝐿 𝑐𝑜𝑠 𝑑𝑥 = 𝑠𝑖𝑛2 =0
𝐿 2𝜋 𝐿
 1
𝐿 2 1/2
2 2 𝑛𝜋𝑥 𝑑 2 𝑛𝜋𝑥
𝑝𝑥2 =න 𝑠𝑖𝑛 −𝑖ℏ 𝑠𝑖𝑛 𝑑𝑥
0 𝐿 𝐿 𝑑𝑥 𝐿 𝐿

2ℏ2 𝐿 𝑛𝜋𝑥 𝑑2 𝑛𝜋𝑥

=− න 𝑠𝑖𝑛 𝑠𝑖𝑛 𝑑𝑥
𝐿 0 𝐿 𝑑𝑥 2 𝐿
2ℏ2 𝑛2 𝜋 2 𝐿 2
𝑛𝜋𝑥
= න 𝑠𝑖𝑛 𝑑𝑥
𝐿3 0 𝐿
2ℏ2 𝑛2 𝜋 2 𝐿 1 1 2𝑛𝜋𝑥
= 3
න ( − cos ) 𝑑𝑥
𝐿 0 2 2 𝐿
= L/2
ℏ2 𝑛2 𝜋 2
=
𝐿2

Extra – Not part of Syllabus

(∆𝑝)2 = 𝑝2 − 𝑝 2

ℏ 2 𝑛2 𝜋 2
(∆𝑝)2 =
𝐿2

Extra – Not part of Syllabus

 Finite Potential Well
• The potential energy is zero
(U(x) = 0) when the particle
is 0 < x < L (Region II)
• The energy has a finite
value (U(x) = U) outside this
region, i.e. for x < 0 and x > L
(Regions I and III)
• We also assume that energy
of the particle, E, is less than
the “height” of the barrier,
i.e. E < U
 Finite Potential Well
Schrödinger Equation
ℏ2 𝜕 2 𝜓 𝑥
− + 𝑈(𝑥)𝜓 𝑥 = 𝐸𝜓 𝑥
2𝑚 𝜕 2 𝑥

I. x < 0; U(x) = U
ℏ2 𝑑 2 𝜓 𝐼
− + 𝑈𝜓𝐼 = 𝐸𝜓𝐼
2𝑚 𝑑𝑥 2

II. 0 < x < L; U(x) = 0

ℏ2 𝑑 2 𝜓𝐼𝐼
− = 𝐸𝜓𝐼𝐼
2𝑚 𝑑𝑥 2

III. x > L; U(x) = U

ℏ2 𝑑 2 𝜓𝐼𝐼𝐼
− + 𝑈𝜓𝐼𝐼𝐼 = 𝐸𝜓𝐼𝐼𝐼
2𝑚 𝑑𝑥 2
 Finite Potential Well: Region II
• U(x) = 0
– This is the same situation as
previously for infinite
potential well
– The allowed wave functions
are sinusoidal
• The general solution is
ψII(x) = F sin kx + G cos kx • The boundary
– where F and G are constants conditions , however,
no longer require that
ψ(x) be zero at the
ends of the well
 Finite Potential Well: Regions I and III
• The Schrödinger equation for these regions is
ℏ2 𝑑 2 𝜓
− + 𝑈𝜓 = 𝐸𝜓
2𝑚 𝑑𝑥 2

• It can be re-written as
𝑑 2 𝜓 2𝑚(𝑈 − 𝐸) 2𝑚(𝑈 − 𝐸)
2 = 2 𝜓 = 𝐶 2 𝜓, where 𝐶 2 ≡
𝑑𝑥 ℏ ℏ2

• The general solution of this equation is

ψ(x) = AeCx + Be-Cx
– A and B are constants
 Finite Potential Well – Regions I and III
ψ(x) = AeCx + Be-Cx
• Requiring that wavefunction was finite at x → ∞ and x → -
∞, we can show that
• In region I, B = 0, and ψI(x) = AeCx
– This is necessary to avoid an infinite value for ψ(x) for large
negative values of x
• In region III, A = 0, and ψIII(x) = Be-Cx
– This is necessary to avoid an infinite value for ψ(x) for large
positive values of x
 Finite Potential Well
• The wavefunction and its derivative must be single-valued
for all x
– At x = 0 and x = L the wave function and its derivative have to be
continuous
• Thus, we have to equate
“parts” of the wavefunction
𝜓I (0) = 𝜓II (0)
and its derivative at x = 0, L 𝑑𝜓I 𝑑𝜓II
– This, together with 0 = 0
𝑑𝑥 𝑑𝑥
normalization condition, 𝜓II (𝐿) = 𝜓III (𝐿)
allows to determine the 𝑑𝜓II 𝑑𝜓III
constants and the equation for 𝐿 = 𝐿
𝑑𝑥 𝑑𝑥
energy of the particle
 ψII(x) = F sin kx + G cos kx

ψI(x) = AeCx
ψIII(x) = Be-Cx
 Finite Potential Well
Graphical Results for ψ (x)
• Outside the potential
well, classical physics
forbids the presence of
the particle
• Quantum mechanics
shows the wave function
decays exponentially to
approach zero
 Finite Potential Well
Graphical Results for Probability
Density, | ψ (x) |2
• The probability densities
for the lowest three
states are shown
• The functions are
smooth at the
boundaries
• Outside the box, the
probability to find the
particle decreases
exponentially, but it is
not zero!
Take home message:
Particle can “leak” into forbidden region.

Comparison with infinite-well potential: The energy of state n

is lower in the finite square well potential of the same width.
 Square Barrier
• Barrier with E<V0
– What is the classical motion of the particle?
 Square Barrier
• In regions I and III we need to solve
ℏ2 𝑑 2 ψ𝐼
− 2
= 𝐸𝜓𝐼
2𝑚 𝑑𝑥
𝑑 2 ψ𝐼 2
2𝑚𝐸
+ 𝑘 𝜓𝐼 = 0 where 𝑘𝐼 = 𝑘𝐼𝐼𝐼 = 𝑘 =
𝑑𝑥 2 ℏ

• In region II we need to solve

ℏ2 𝑑 2 ψ𝐼𝐼
− + 𝑉0 ψ𝐼𝐼 = 𝐸𝜓𝐼𝐼
2𝑚 𝑑𝑥 2
𝑑 2 ψ𝐼𝐼 2
2𝑚 𝑉0 − 𝐸
− 𝜅𝐼𝐼 𝜓𝐼𝐼 = 0 where 𝜅𝐼𝐼 = 𝜅 =
𝑑𝑥 2 ℏ
 Square Barrier
• The solution in Region I contains the incident
and reflected wave
𝜓I = 𝐴𝑒 𝑖𝑘𝑥 + 𝐵𝑒 −𝑖𝑘𝑥

• The solution in Region III contains the

transmitted wave
𝜓III = 𝐸𝑒 𝑖𝑘𝑥 + 𝐹𝑒 −𝑖𝑘𝑥 → 𝐸𝑒 𝑖𝑘𝑥

• The solution in Region II is

𝜓II = 𝐶𝑒 𝜅𝑥 + 𝐷𝑒 −𝜅𝑥
 Square Barrier

𝑇 = 𝑒 −2𝜅𝐿
2𝑚 𝑉0 −𝐸
Where, 𝜅 =
ℏ
66
 Square Barrier
• Thus we get a finite transmission probability T even though E
< V0
– This is called tunneling

𝑇 = 𝑒 −2𝜅𝐿
The exponential shows the importance of the barrier width L over
the barrier height V0
 STM
• Tunneling through the potential barrier
69
 The Harmonic Oscillator
Simple Harmonic Motion from the View of Quantum Mechanics

In order to know the wave function that describe the harmonic vibrational moti
on for the simple harmonic oscillator and the allowed energy levels, we have to
solve the Schrödinger equation
෡ = 𝐸𝜓
𝐻𝜓
the Hamiltonian operator is given by
𝐻෡ = 𝑇෠ + 𝑉෠
the kinetic energy operator is given by
ℏ2 𝑑 2
𝑇෠ = −
2𝜇 𝑑𝑥 2
notice that, we are assuming that the motion of the simple harmonic oscillator (
e.g. the vibration of a diatomic molecule) is in one direction and we assumed th
at the motion is along the 𝑥 − 𝑎𝑥𝑖𝑠.
The potential energy operator
1 2
෠
𝑉 = 𝑘𝑥
2
 The Harmonic Oscillator
Now substituting 𝑇෠ and 𝑉෠ into the one-dimensional Schrödinger equation gives
ℏ2 𝑑 2 𝜓 𝑥 1
− + 𝑘𝑥 2 𝜓 𝑥 = 𝐸 𝜓 𝑥
2𝜇2 𝑑𝑥 2 2

After some effort, the eigenfunctions are

𝟏 (𝜶𝒙)𝟐
𝝍𝝊 𝑥 = 𝑵𝝊 𝑯𝝊 𝜶 𝒙 𝟐 𝒆− 𝟐 𝜐 = 0, 1, 2, …
H

where 𝑯𝝊 is the Hermite polynomial of degree 𝜐.

𝜶 is defined as:
2𝜋𝜇𝜈
𝛼=
ℏ
𝑵𝝊 is the normalization constant which is defined as:
1 𝑦 = 𝛼𝑥
1
−2 𝛼 4
𝑁𝜐 = 2𝜐 𝜐!
𝜋
 The Harmonic Oscillator
The eigenvalues are
𝟏
𝑬𝝊 = 𝝊 + 𝒉𝛎 𝜐 = 0, 1, 2, 3, …
𝟐

where 𝜐 the quantum number 𝜐.

Notice that, the energy is restricted to the quantized values

Recall that,
𝜔 1
𝜈= and 𝜔= 𝑘/𝜇 ⇒ 𝜈 = 2𝜋 𝑘/𝜇
2𝜋
And
ℎ
ℏ= ⇒ ℎ = ℏ 2𝜋
2𝜋

Therefore,
1
1
𝐸𝜐 = ℏ 𝑘/𝜇 2 𝜐 +
2

𝟏
𝑬𝝊 = ℏ𝝎 𝝊 +
𝟐
The Harmonic Oscillator

(a) The normalized harmonic-oscillator wave functions.

(b) The probability densities for a harmonic oscillator.
74
Extra – Not part of Syllabus
 Chapter 6
Hydrogen Atom
The Schrödinger equation in 3-D
• Electrons in an atom can move in all three dimensions of space. If
a particle of mass m moves in the presence of a potential energy
function U(x, y, z), the Schrödinger equation for the particle’s
wave function (x, y, z, t) is
ℏ2 𝜕 2 Ψ 𝑥, 𝑦, 𝑧, 𝑡 𝜕 2 Ψ 𝑥, 𝑦, 𝑧, 𝑡 𝜕 2 Ψ 𝑥, 𝑦, 𝑧, 𝑡
− 2
+ 2
+
2𝑚 𝜕𝑥 𝜕𝑦 𝜕𝑧 2
𝜕Ψ 𝑥, 𝑦, 𝑧, 𝑡
+𝑈 𝑥, 𝑦, 𝑧 Ψ 𝑥, 𝑦, 𝑧, 𝑡 = 𝑖ℏ
𝜕𝑡

• This is a direct extension of the one-dimensional Schrödinger

equation.
The Schrödinger equation in 3-D: Stationary states
• If a particle of mass m has a definite energy E, its wave function (x, y, z, t) is a
product of a time-independent wave function (x, y, z) and a factor that
depends on time but not position. Then the probability distribution function
• |(x, y, z, t)|2 = |(x, y, z)|2 does not depend on time (stationary states).
Ψ 𝑥, 𝑦, 𝑧, 𝑡 = 𝜓 𝑥, 𝑦, 𝑧 𝑒 −𝑖𝐸𝑡/ℏ

• The function (x, y, z) obeys the time-independent Schrödinger equation in

three dimensions:

ℏ2 𝜕 2 𝜓 𝑥, 𝑦, 𝑧 𝜕 2 𝜓 𝑥, 𝑦, 𝑧 𝜕 2 𝜓 𝑥, 𝑦, 𝑧
− + +
2𝑚 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
+𝑈 𝑥, 𝑦, 𝑧 𝜓 𝑥, 𝑦, 𝑧 = 𝐸𝜓 𝑥, 𝑦, 𝑧

• The normalization of the three-dimensional wave function probability

distribution function is
2
න 𝜓 𝑥, 𝑦, 𝑧 𝑑𝑉 = 1
Particle in a three-dimensional box
• In analogy with our infinite square-well potential (U(x) = 0 inside, U(x) = ∞
outside), let us consider a three-dimensional region in space (box) of equal
sides of length L, with the same potential (U(x) = 0 inside, U(x) = ∞ outside).
• We will consider the wave function as separable, that is, can be written as a
product of the three independent dimensions x, y and z:
𝜓 𝑥, 𝑦, 𝑧 = 𝑋(𝑥)𝑌(𝑦)𝑍(𝑧)

• The Schrödinger equation inside the box becomes

ℏ2 𝜕2𝑋 𝑥 𝜕2𝑌 𝑦 𝜕2𝑍 𝑧
− 𝑌(𝑦)𝑍(𝑧) + 𝑋(𝑥)𝑍(𝑧) + 𝑋(𝑥)𝑌(𝑦) = 𝐸𝑋(𝑥)𝑌(𝑦)𝑍(𝑧)
2𝑚 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2

• Or, dividing by X(x)Y(y)Z(z) we have:

ℏ2 1 𝜕2𝑋 𝑥 1 𝜕 2𝑌 𝑦 1 𝜕2𝑍 𝑧
− + + =𝐸
2𝑚 𝑋(𝑥) 𝜕𝑥 2 𝑌(𝑦) 𝜕𝑦 2 𝑍(𝑧) 𝜕𝑧 2
Particle in a three-dimensional box
• This says that the total energy is contributed to by three terms on the left, each
depending separately on x, y and z. Let us write E = Ex + Ey + Ez. Then this
equation can be separated into three equations:
ℏ2 𝜕 2 𝑋 𝑥
− = 𝐸𝑋 𝑥
2𝑚 𝜕𝑥 2
ℏ2 𝜕 2 𝑌 𝑦
− = 𝐸𝑌 𝑦
2𝑚 𝜕𝑦 2
ℏ2 𝜕 2 𝑍 𝑧
− = 𝐸𝑍 𝑧
2𝑚 𝜕𝑧 2

• These obviously have the same solutions separately as our original particle in
an infinite square well, and corresponding energies:
𝑛𝑋 𝜋𝑥 𝑛𝑋 2 𝜋 2 ℏ2
𝑋𝑛𝑋 (𝑥) = 𝐶𝑋 sin (𝑛𝑋 = 1,2,3. . . ) 𝐸𝑋 = (𝑛𝑋 = 1,2,3. . . )
𝐿 2𝑚𝐿2
𝑛𝑌 𝜋𝑦 𝑛𝑌 2 𝜋 2 ℏ 2
𝑌𝑛𝑌 (𝑦) = 𝐶𝑌 sin (𝑛𝑌 = 1,2,3. . . ) 𝐸𝑌 = (𝑛𝑌 = 1,2,3. . . )
𝐿 2𝑚𝐿2
𝑛𝑍 𝜋𝑧
𝑍𝑛𝑍 (𝑧) = 𝐶𝑍 sin (𝑛𝑍 = 1,2,3. . . ) 𝑛𝑍 2 𝜋 2 ℏ 2
𝐿 𝐸𝑍 = (𝑛𝑍 = 1,2,3. . . )
2𝑚𝐿2
Particle in a three-dimensional box
• A particle’s wave-function is the product of these three solutions,
𝑛𝑋 𝜋𝑥 𝑛𝑌 𝜋𝑦 𝑛𝑍 𝜋𝑧
𝜓 𝑥, 𝑦, 𝑧 = 𝑋(𝑥)𝑌(𝑦)𝑍(𝑧) = 𝐶 sin sin sin
𝐿 𝐿 𝐿

• We can use the three quantum numbers nX, nY, and nZ to label the stationary
states (states of definite energy). Here is an example of a particle in three
possible states (nX, nY, nZ) = (2, 1, 1), (1, 2, 1) or (1, 1, 2).
• The three states shown here are degenerate: Although they have different
values of nX, nY, and nZ, they have the same total energy E.
4𝜋 2 ℏ2 𝜋 2 ℏ2 𝜋 2 ℏ2 3𝜋 2 ℏ2
𝐸 = 𝐸𝑋 + 𝐸𝑌 + 𝐸𝑍 = + + =
2𝑚𝐿2 2𝑚𝐿2 2𝑚𝐿2 𝑚𝐿2
Particle in a three-dimensional box
Example: (a) Find the value of the normalization constant C. (b) Find the
probability that the particle will be found somewhere in the region 0 ≤ x ≤ L/4, for
the cases (nX, nY, nZ) = (1, 2, 1), (2, 1, 1) and (3, 1, 1).

𝐿 𝐿 𝐿
2 2
𝑛𝑋 𝜋𝑥 2
𝑛 𝜋𝑦
2 𝑌
𝑛𝑍 𝜋𝑧
න 𝜓 𝑥, 𝑦, 𝑧 𝑑𝑉 = 𝐶 න sin 𝑑𝑥 න sin 𝑑𝑦 න sin2 𝑑𝑧 = 1
0 𝐿 0 𝐿 0 𝐿

1
sin2 𝜃 = (1 − cos 2 𝜃)
2
𝐿 𝐿
𝑛𝑋 𝜋𝑥 𝐿 𝑛𝑋 𝜋𝑥 1 2𝑛𝑋 𝜋𝑥 𝐿
න sin2 𝑑𝑥 = − sin =
0 𝐿 2𝑛𝑋 𝜋 𝐿 2 𝐿 0
2

3 𝐿/4 𝐿 𝐿
2 𝜋𝑥 2𝜋𝑦 𝜋𝑧
න 𝜓 𝑥, 𝑦, 𝑧 2 𝑑𝑉 = න 2
sin 𝑑𝑥 න sin 2
𝑑𝑦 න sin2 𝑑𝑧
𝐿 0 𝐿 0 𝐿 0 𝐿

𝐿/4 𝐿/4 3
𝜋𝑥 𝐿 𝜋𝑥 1 2𝜋𝑥 𝐿 𝐿 2 𝐿 𝐿 𝐿 𝐿
න sin2 𝑑𝑥 = − sin = − so − = 0.091
0 𝐿 2𝜋 𝐿 2 𝐿 0
8 4𝜋 𝐿 8 4𝜋 2 2
Energy Degeneracy
• For a particle in a three-dimensional box, the allowed energy levels are
surprisingly complex. To find them, just count up the different possible states.
• Here are the first 6 for an equal-sided box:

3𝜋 2 ℏ2 6-fold degenerate
𝐸1,1,1 =
2𝑚𝐿2
Not degenerate
3-fold degenerate

3-fold degenerate

3-fold degenerate

If length of sides of box are different:

𝑛𝑋 2 𝑛𝑌 2 𝑛𝑍 2 𝜋 2 ℏ2 Not degenerate
𝐸= + +
𝐿𝑋 2 𝐿𝑌 2 𝐿𝑍 2 2𝑚
(breaks the degeneracy)
 SCHRÖDINGER’S EQUATION FOR THE HYDROGEN ATOM

a) Spherical polar coordinates.

(b) A line of constant zenith angle  on a sphere is a circle whose plane is perpendicular to
the z axis.
(c) A line of constant azimuth angle  is a circle whose plane includes the z axis.
In spherical polar coordinates Schrödinger’s equation is written
 Solving the polar Schrödinger equation gives three quantum numbers. These
Q# are required to describe the electron in a hydrogen atom, in place of the
single quantum number of the Bohr theory.

The third term is a function of azimuth angle  only, whereas the other terms are
functions of r and  only.
 Rearrange

The differential equation for the function  is therefore

Each of these is an ordinary differential equation for a single function of a single
variable.
Only the equation for R depends on the potential energy U(r).
 Description of solution
• We will not go through the mathematics of the
solution, but note that we can only accept solutions for
which the wave function is normalizable (does not
blow up).
• Some radial solutions blow up at r = 0 or r = ∞, and
so must be discarded. As in the harmonic oscillator
problem, the radial solutions R(r) turn out to be an
exponential function e−r, multiplied by a polynomial
in r.
• The angular solutions () are polynomials
containing powers of sin and cos.
• The azimuthal solutions () have to be periodic
(have the same value at () and (+2), etc. They
turn out to depend on eiml, where ml is an integer,
either positive, negative or zero.
The solution for the radial part R(r) of the hydrogen atom wave function Ψ also
requires that a certain condition be fulfilled. This condition is that E be positive or
have one of the negative values En (signifying that the electron is bound to the atom)
specified by

The same formula for the

energy levels of the hydrogen
atom that Bohr obtained.
PRINCIPAL QUANTUM NUMBER
Quantization of energy ➔ n is quantized

ORBITAL QUANTUM NUMBER

If the last two terms in the square brackets of the equation cancel each other out,
we have a differential equation for R(r) that involves functions of the radius vector
r exclusively.
 Since the orbital kinetic energy of the electron and the magnitude of its angular
momentum are

The orbital kinetic energy

Compare above with

Like total energy E, angular momentum is both conserved and quantized.

Designation of Angular-Momentum States
It is customary to specify electron angular-momentum states by a letter, with s
corresponding to l = 0, p to l = 1, and so on, according to the following scheme:
MAGNETIC QUANTUM NUMBER
If the magnetic-field direction be parallel to the z axis, the component of L in z
direction is
ELECTRON PROBABILITY DENSITY
The probability density |Ψ|2 that corresponds to the electron wave function
Ψ = RΘΦ in the hydrogen atom is

Probability of Finding the Electron

𝜋 2𝜋
𝑃 𝑟 𝑑𝑟 = 𝑟 2 𝑅∗ 𝑟 𝑅 𝑟 𝑑𝑟 න |Θ|2 𝑠𝑖𝑛𝜃𝑑𝜃 න |Φ|2 𝑑∅ = 𝑟 2 |𝑅|2 𝑑𝑟
0 0
 𝜋 2𝜋
𝑃 𝑟 𝑑𝑟 = 𝑟 2 𝑅∗ 𝑟 𝑅 𝑟 𝑑𝑟 න |Θ|2 𝑠𝑖𝑛𝜃𝑑𝜃 න |Φ|2 𝑑∅ = 𝑟 2 |𝑅|2 𝑑𝑟
0 0
• The most probable value of 𝑟 for a 1𝑠 electron is 𝑎0​, the orbital radius of a ground-
state electron in the Bohr model.

• The average value of r for a 1s electron is 1.5a0.

Angular Variation of Probability Density
The hydrogen atom: Probability distributions I
• States of the hydrogen atom with l = 0 (zero orbital angular
momentum) have spherically symmetric wave functions that
depend on r but not on  or . These are called s states.
• Figure below shows the electron probability distributions for three
of these states.

https://winter.group.shef.ac.uk/orbitron/atomic_orbitals/1s/index.html
The hydrogen atom: Probability distributions II
• States of the hydrogen atom with nonzero orbital angular
momentum, such as p states (l = 1) and d states (l = 2), have wave
functions that are not spherically symmetric.
• Figure below shows the electron probability distributions for
several of these states, as well as for two spherically symmetric s
states.
The hydrogen atom: Degeneracy
• States with different quantum numbers l and n
are often referred to with letters as follows:
l value letter
0 s
n value shell
1 p
1 K
2 d
2 L
3 f
3 M
4 g
4 N
5 h

• Hydrogen atom states with the same value of n

but different values of l and ml are degenerate
(have the same energy).
• Figure → shows radial probability distribution
for states with l = 0, 1, 2, 3 and different values
of n = 1, 2, 3, 4.
 RADIATIVE TRANSITIONS

Bohr postulated that the frequency of the radiation emitted by an atom dropping
from an energy level Em to a lower level En is
The expectation value <x> of the position of such an electron is
An electron that shifts from one energy state to another

a*a = probability that the electron in state n

b*b = probability that the electron in state m

a*a + b*b = 1
Initially a=1 and b = 0;
when the electron is in the excited state→ a=0 and b = 1; and ultimately a = 1
and b = 0 once more.
While the electron is in either state, there is no radiation, but when it is in the
midst of the transition from m to n (that is, when both a and b have
nonvanishing values), electromagnetic waves are produced.
The expectation value <x> that corresponds to the composite wave function

let a*a=a2 and b*b = b2.

The first and last integrals do not vary with time, so the second and third
integrals are the only ones able to contribute to a time variation in <x>.
The electron’s position therefore oscillates sinusoidally at the frequency

• When the electron is in state n or state m the expectation value of the electron’s
position is constant.
• When the electron is undergoing a transition between these states, its position
oscillates with the frequency .
• Such an electron, of course, is like an electric dipole and radiates electromagnetic
waves of the same frequency .
• This result is the same as that postulated by Bohr and verified by experiment.
SELECTION RULES

The general condition necessary for an atom in an excited state to radiate is that the
integral

not be zero

Integral is finite → allowed transitions

Integral is zero → forbidden transitions

In the case of the hydrogen atom, three quantum numbers are needed to specify the
initial and final states involved in a radiative transition. If the principal, orbital, and
magnetic quantum numbers of the initial state are n’, l’, m’l, respectively, and those
of the final state are n, l, ml, and u represents either the x, y, or z coordinate, the
condition for an allowed transition is
Since the wave functions n,l,ml for the hydrogen atom are known, the allowed
transitions can be evaluated for u = x, u = y, and u = z for all pairs of states
differing in one or more quantum numbers.

When this is done, it is found that the only transitions between states of different n
that can occur are those in which the orbital quantum number l changes by 1 or −1
and the magnetic quantum number ml does not change or changes by 1 or −1.

The change in total quantum number n is not restricted.

ZEEMAN EFFECT
H atom in an external magnetic field → semiclassical model
the electron motion is described by a classical circular orbit, while the
angular momentum is given by the quantum mechanical expression

velocity

The current causes a magnetic moment

The angular momentum of the circulating electron is

Since μ is proportional to l, the orbital magnetic moment is

often labeled μl .
In an external magnetic field the potential energy of a magnetic dipole with magnetic
moment μ is

When the magnetic field points into the z-direction (B = {0, 0,

Bz = B}), because of lz = mℏ,

where m (the projection of l onto the z-axis) is called the magnetic quantum number,
It can take values −l ≤ m ≤+l.
→ Bohr magneton

The additional energy caused by the magnetic field as

This gives for the energies of the hydrogen atomic states in an external magnetic field
The 2𝑙 + 1 m-sublevels that are degenerate
without magnetic field split into 2𝑙 + 1
equidistant Zeeman components with energies
between
𝐸𝑛𝑚𝑖𝑛 = 𝐸𝑐𝑜𝑢𝑙 𝑛 − 𝜇𝐵 𝑚𝐵
𝐸𝑛𝑚𝑎𝑥 = 𝐸𝑐𝑜𝑢𝑙 𝑛 + 𝜇𝐵 𝑚𝐵

With an energetic distance

∆𝐸 = 𝐸𝑛,𝑙,𝑚 − 𝐸𝑛,𝑙,𝑚−1 = 𝜇𝐵 𝐵 Zeeman splitting of a level with
l=2 in a homogeneous magnetic
between adjacent levels which is determined
field (normal Zeeman effect)
by the product of Bohr Magneton 𝜇𝐵 and
magnetic field strength B.
𝑒ℏ
𝜇𝐵 =
2𝑚𝑒
The Zeeman effect and selection rules
• Lower left figure shows the shift in energy of the five l = 2 states (each
with a different value of ml) as the magnetic field strength is increased.
• An atom in a magnetic field can make transitions between different
states by emitting or absorbing a photon A transition is allowed if l
changes by 1 and ml changes by 0, 1, or –1. (This is because a photon
itself carries angular momentum.) A transition is forbidden if it violates
these selection rules.