Introduction

 Failure of classical mechanics

 Black body radiation
 Non relativistic motion of electrons
 Radiation of energy from excited atom
 Hydrogen spectrum
 Classical mechanics – motion of objects which are directly observable
or observable with help of inst. like microscope.
 Classical concepts do not hold good at atomic dimensions.
 matter concerning all these phenomena constitute quantum physics.
 The currently accepted basic mathematical theory of quantum physics
is called quantum mechanics.
 Inadequacy of classical mechanics

1. Electrons moving round the nucleus – according to

classical theory – electron losses energy and ultimately
collapses showing instability of atom but not witnessed.
(fails to explain the stability of atom)
2. CM fails to explain the spectrum of exited hydrogen
atom, photoelectric effect, blackbody radiation
 The Birth of Quantum Mechanics
___________________________

 There were several experimental observations

which could not be explained by the
established laws of classical physics and called
for a radically different way of thinking

 This lead to the development of Quantum

Mechanics which is today regarded as the
fundamental theory of Nature.
Some key events/observations that lead to the
development of quantum mechanics…

 Black body radiation spectrum (Planck, 1901)

 Photoelectric effect (Einstein, 1905)
 Model of the atom (Rutherford, 1911)
 Quantum Theory of Spectra (Bohr, 1913)
 Scattering of photons off electrons (Compton, 1922)
 Exclusion Principle (Pauli, 1922)
 Matter Waves (de Broglie 1925)
 Experimental test of matter waves (Davisson and Germer,
1927)
 Dual nature of light

 Wave (electromagnetic) - Interference

- Diffraction

 Particle (photons) - Photoelectric effect

- Compton effect

Wave - Particle Duality for light

 History

Light is a beam Exhibits interference,

of particles hence waves!

Newton Huygens
EM Theory,
hence waves

In photoelectric effect, light Maxwell

Einstein behaves like particles

In my scattering expts,
light - beam of particles
Compton
 What about Matter?
_______________________________

If light, which was traditionally understood

as a wave also turns out to have a particle
nature, might matter, which is traditionally
understood as particles, also have a wave
nature?

Yes!
 Wave Nature of Matter
Louis de Broglie in 1923 proposed that matter
particles should exhibit wave properties just as
light waves exhibited particle properties. These
waves have very small wavelengths in most
situations so that their presence was difficult
to observe.
 Louis de Broglie’s hypothesis

The dual nature of matter

A particle with momentum p has a matter

wave associated with it, whose
wavelength is given by
h

p
 Derivation
 Energy of photon E = hν, or (E = ħ or p = ħk planck-
Einstein relations)
 using relativistic expression, energy of photon is given by
E = mc2 (p = mass x velocity)

 From the above equations

mc2 = hν
mc2 = hc/ λ
mc = h/ λ
mv = h/ λ
p = hν / c
p=h/λ λ=c /ν
Therefore
 momentum of particle with mass m and velocity v is
given by
p = mv
and its debroglie wavelength is given by
λ = h / mv (since  = h / p)

In the above equation m is the relativistic mass given by

m = m0 / [1-(v2/c2)]1/2
de Broglie wavelength expressed in terms of K.E or
(energy)
w.k.t.
E = (1/2) mv2 implies mv = (2mE)1/2
but λ = h / mv substituting for mv
λ = h / (2mE)1/2
de Broglie wavelength expressed in terms of voltage

 A charged particle with charge q is accl. through a

potential diff. V then K.E
E =qV
and de Broglie wavelength
λ = h / (2mqV)1/2 sub. for E from above
Therefore
The de Broglie expression for an electron in a non-
relativistic case will be
λ = h / (2m0eV)1/2 e – charge of an
electron
The connecting link – Planck’s constant

Dual Nature

Radiation E  h
h
Matter 
p
 Properties of matter waves
All moving objects will be having wave nature
Smaller the velocity, greater the wavelength
Lesser is the mass, greater is the wavelength
Wave velocity is greater than light velocity
If velocity is zero, it exhibit particle nature
If velocity is infinite, the wavelength is indefinite
Uncertainty in finding the position and momentum
Why isn’t the wave nature of matter more
apparent to us…?
___________________________________


h6
.6x
10J.s 34

Planck’s constant is so small that we don’t

observe the wave behaviour of ordinary objects
– their de Broglie wavelengths could be many
orders of magnitude smaller than the size of a
nucleus!
 Heisenberg's Uncertainty Principle
___________________________________
 The Uncertainty Principle is an important consequence
of the wave-particle duality of matter and radiation
and is inherent to the quantum description of nature

 Simply stated, it is impossible to know both the exact

position and the exact momentum of an object
simultaneously
A fact of Nature!
 Heisenberg realised that ...
 In the world of very small particles, one cannot
measure any property of a particle without
interacting with it in some way
 This introduces an unavoidable uncertainty into
the result
 One can never measure all the
properties exactly

Werner Heisenberg (1901-1976)

 Measuring the position and momentum
of an electron
 Shine light on electron and detect reflected
light using a microscope
 Minimum uncertainty in position
is given by the wavelength of the
light
 So to determine the position
accurately, it is necessary to use
light with a short wavelength
 Heisenberg’s Uncertainty Principle

If a measurement of position of a particle is made with precision Δx

and a simultaneous measurement of linear momentum is made with

precision Δp then the product of the two uncertainties can never be
smaller than h/4
The more accurately you know the position (i.e.,
the smaller Dx is) , the less accurately you know the momentum
(i.e., the larger Dp is); and vice versa
 Implications
 It is impossible to know both the position and
momentum exactly, i.e., Dx=0 and Dp=0

 These uncertainties are inherent in the physical world

and have nothing to do with the skill of the observer

 Because h is so small, these uncertainties are not

observable in normal everyday situations
 Heisenberg’s Uncertainty Principle
involving energy and time

 The more accurately we know the energy of a body,

the less accurately we know how long it possessed
that energy
 Derivation for uncertainty in energy and time
h
position momentum relation D xD p x 
4
m  p h
 
multiply and divide above eqn. by m & p Dx Dpx   
 p  m  4

From Einstein’s equation E = p2/2m (since E = ½ mv2 and p = mv)

∆ E = ∆ p 2p/2m
= ∆ p (p/m)
Further ∆ x (m/p) = ∆ x / v = ∆ t since p = mv
Substituting for ∆ x (m/p) and ∆ p (p/m) in position –
momentum equation we get h
DEDt 
4
 Heisenberg's Uncertainty Principle
___________________________________

Position & momentum h

DxDp x 
4
h
Energy & time DEDt 
4
 Applications of Heisenberg principle

 Non existence of electrons in nucleus

 Binding energy of an electron
 Strength of nuclear forces
 Radiation from excited atom
 Davisson-Germer Experiment
• By accident, Davisson and Germer found that
electrons were diffracted by large nickel crystals,
similar to diffraction of light by crystals

PHYS140 Matter Waves 25

Davisson and Germer -- VERY clean nickel crystal.
Interference is electron scattering off Ni atoms.

e e e
e e det.
e
scatter off atoms
e e
e e e
e
move detector around,
see what angle electrons coming off
Ni
Davisson-Germer experiment
 See peak!!

so probability of angle where detect

# e’s electron determined by interference
of deBroglie waves!
0 500
scatt. angle 
e
e
e e e
e det. e
Observe pattern of scattering
e electrons off atoms
e Looks like ….
Wave!

Ni
Results
 ELECTRON DIFFRACTION
The Davisson-Germer experiment (1927)

G.P.
The Davisson-Germer Davisson Thomson
θi experiment: scattering a beam
of electrons from a Ni crystal.
Davisson got the 1937 Nobel
prize.
θi

At fixed angle, find sharp peaks in

intensity as a function of electron
energy
Davisson, C. J.,
At fixed accelerating voltage "Are Electrons
(fixed electron energy) find a Waves?,"
pattern of sharp reflected beams Franklin
from the crystal Institute
Journal 205,
597 (1928)
G.P. Thomson performed similar
interference experiments with thin-
film samples
 ELECTRON DIFFRACTION (cont)

Interpretation: similar to Bragg scattering of X-rays from

crystals

θi Path
a cos i difference:
a(cos r  cos i )
θr
Constructive interference
a
when
a(cos r  cos i )  n

Electron scattering
dominated by
surface layers a cos  r Note difference from usual “Bragg’s
Law” geometry: the identical
Note θi and θr not scattering planes are oriented
necessarily equal perpendicular to the surface
 The Compton Effect
 Compton directed a beam of X-rays toward a block of
graphite
 He found that the scattered X-rays had a slightly
longer wavelength that the incident x-rays
 This means they also had less energy

 The amount of energy reduction depended on the

angle at which the X-rays were scattered
 The change in wavelength is called the Compton shift
 Compton
COMPTON SCATTERING
Compton (1923) measured intensity of scattered X-rays from
solid target, as function of wavelength for different angles.
He won the 1927 Nobel prize.

X-ray source
Collimator Crystal
(selects angle) (selects
wavelength)

θ
Target

Detector
Result: peak in scattered radiation
shifts to longer wavelength than source.
Amount depends on θ (but not on the
target material).
 COMPTON SCATTERING (cont)
Change in wavelength of scattered light is completely
unexpected classically

Incident light wave Oscillating electron Emitted light wave

Compton’s explanation: “billiard ball” collisions between particles of

light (X-ray photons) and electrons in the material

Before After p 
scattered photon
Incoming photon φ

p Electron θ
pe scattered electron
 Compton Scattering

 Compton assumed the photons acted like other

particles in collisions
 Energy and momentum were conserved
 The shift in wavelength is

λ’ - λ = (h / m0c) (1- cosφ)

 Analyzed as interaction bet’ single photon and an electron assumed
to be at rest
 Photon with energy hν collide elastically with free electron in the
scattering substance
 Incident photon transfers energy to electron – electron acquires KE
and recoils with velocity ‘v’ – scattered photon with energy hν’.
Applying laws of conservation of energy and
conservation of momentum we can calculate the
compton shift
 Momentum before collision:

 x-component of the momentum

Momentum of the photon = hν/c

Momentum of the electron = 0

Total momentum along the x-axis = hν/c

 y-component of the momentum:

Initial momentum of the photon = 0

Initial momentum of the electron= 0

Total momentum along the y-axis = 0

 Applying law of conservation of momentum (separately for x and y component)

hν/c = [hν’ cosφ/c] + mv cosθ (2)

0 = [hν’ sinφ/c] – mv sinθ (3)

Rearranging eqn 2

hν/c - [hν’ cosφ/c] = mv cosθ

h (ν - ν’ cosφ) = mvc cosθ (4)
Rearranging eqn. 3
[hν’ sinφ] = mvc sinθ (5)
Squaring and adding eqn. 4 & 5
[h2 (ν2 + ν’2 cos2φ - 2 νν’ cosφ) + h2 ν’2 sin2φ = m2v2c2 (cos2 θ+ sin2 θ)
h2(ν2 - 2 νν’ cosφ + ν’2 cos2φ + ν’2 sin2φ ) = m2v2c2 as (cos2φ + sin2φ = 1)
h2(ν2 - 2 νν’ cosφ + ν’2) = m2v2c2 (6)
 From eqn. 1 (conservation of energy)

h ν+ m0 c2= hν’+mc2
mc2 = h ν - hν’ + m0 c2
mc2 = h (ν - ν’) + m0 c2
squaring the above equation
m2c4 = [h (ν - ν’) + m0c2]2
m2c4 = h2 (ν - ν’)2 + 2h (ν - ν’) m0c2 + m02c4
m2c4 = h2(ν2 + ν’2 - 2 νν’) + 2h (ν - ν’) m0c2 + m02c4 (7)
Subtracting eqn. 6 from eqn. 7
m2c4 - m2v2c2 = [h2ν2 + h2ν’2 - 2h2 νν’ + 2h (ν - ν’) m0c2 +
m02c4 - h2ν2 + 2 h2νν’ cosφ - h2ν’2]
m2c2 ( c2-v2) = [- 2h2 νν’ + m02c4 + 2 h2νν’ cosφ + 2h (ν - ν’)
m0c2 ]
m2c2 ( c2-v2) = m02c4 - 2h2 νν’(1- cosφ)+ 2h (ν - ν’) m0c2 (8)
According to theory of relativity
m = m0/ [1-(v2/c2)]1/2
Squaring and rearranging
m2 = m02/ [1- (v2/c2)]
m2 = m02/ [(c2- v2)/c2]
m2 = m02 c2 / (c2- v2)
m2 (c2- v2) = m02 c2
Multiplying the above equation by c2
m2 c2(c2- v2) = m02 c4 (9)
Substituting for m2 c2(c2- v2) in eqn. 8
m02 c4 = - 2h2 νν’(1- cosφ)+ 2h (ν - ν’) m0c2 + m02c4
2h (ν - ν’) m0c2 = 2h2 νν’(1- cosφ)
(ν - ν’) / νν’= [2h2 (1- cosφ)] / 2h m0c2
(ν - ν’) / νν’= (h / m0c2) (1- cosφ)
(ν - ν’) / νν’= (h / m0c2) (1- cosφ)
the above equation can be written as
(1/ν’) – (1/ ν) = (h / m0cc) (1- cosφ)
Taking one c to LHS
(c/ν’) – (c/ ν) = (h / m0c) (1- cosφ) since c = ν λ
λ’ - λ = (h / m0c) (1- cosφ)
d λ = (h / m0c) (1- cosφ)
from the above eqn. it is evident that compton shift dλ is independent
of wavelength of the incident radiation as well as the nature of the
scattering substance. It depends only on angle of scattering.
Case 1 : when φ = 0, cosφ = 1 hence change in wavelength dλ = 0
Case 2 : when φ = 90°, cosφ = 0
Then d λ = (h / m0c)
Substituting the values for h, m0 and c
d λ = (6.625 x 10-34) / (9.1 x 10-31 x 3 x 108) = 0.02425 Å
Case 3 : when φ = 180°, cos φ = -1
therefore d λ = 2h/ m0c
d λ = 2[(6.625 x 10-34) / (9.1 x 10-31 x 3 x 108)]
= 0.0485 Å
which implies that when φ = 180°, d λ is maximum.

Compton’s experiments showed

that, at any given angle, one
additional frequency of
radiation is observed
Schrodinger wave equations
 Schrodinger: A prologue
Inferring the Wave-equation for Light

… so relating ω to k allows us to infer the wave-equation

 Schrodinger: A Wave Equation for Electrons

Schrodinger guessed that there was some wave-like quantity

that could be related to energy and momentum …

wavefunction
Schrodinger: A Wave Equation for Electrons

(free-particle)

(free-particle)

..The Free-Particle Schrodinger Wave Equation !

Erwin Schrödinger (1887–1961)

Image in the Public Domain
 Classical Energy Conservation

Maximum height
and zero speed
Zero speed start

Fastest

 total energy = kinetic energy + potential energy

 In classical mechanics,

 V depends on the system

 e.g., gravitational potential energy, electric potential energy
 Schrodinger Equation and Energy Conservation
... The Schrodinger Wave Equation !

Total E term K.E. term P.E. term

... In physics notation and in 3-D this is how it looks:

Electron
Maximum height Potential
and zero speed Energy
Zero speed start

Incoming
Electron

Fastest Battery
 Time-Dependent Schrodinger Wave Equation

Total E K.E. term P.E. term

PHYSICS term
NOTATION

Time-Independent Schrodinger Wave Equation

  Matter waves – waves of what?
 Water waves – quantity that varies periodically is the height of the water surface
 Sound waves – pressure
 Light waves – variation of electric and magnetic field
 Matter waves - ???????
 Quantity whose variation make up matter waves is called the wave function “ Ψ ”
 The value of wave function “ Ψ ” associated with the moving body at the particular
point x, y, z in space at time t is related to the likely hood of finding the body there
at the time.
 “ Ψ ” – has no direct physical significance – because it cannot be interpreted in
terms of an experiment –
 Probability of finding a particle at a point lies between 0 and 1 but how about the fraction
0.2 – 20% chance of finding the object
 Amplitude of the wave - +ve as well as –ve – negative probability is meaningless, hence
“ Ψ ” itself is not an observable quantity.
 The objection does not apply to ‫׀‬Ψ ‫׀‬2, the square of the absolute value of the wave
function, which is known as Probability density.
 The probability of experimentally finding the body described by the wave function Ψ at
the point x, y, z at the time t is proportional in the value of ‫׀‬Ψ ‫׀‬2 there at t.

 Large value of ‫׀‬Ψ ‫׀‬2 – strong possibility, small values – slight possibility of its
presence.
 As ‫׀‬Ψ ‫׀‬2 is not actually zero somewhere, however there is a definite chance ,
however small, of detecting it there. First made by Max Born in 1926.

 Describing a wave
 General formula of waves
 How fast do de Broglie waves travel? (to us an ironical statement)

 As de Broglie wave is associated with moving body, we expect that this wave have
the same velocity of that of the body – to be justified.
 If we call de Broglie wave velocity vp, we can apply the usual formula to find vp

vp = 
 The wavelength  is the de broglie wave length  = h/mv
 To find the frequency, we equate the quantum expression E = h with the relativistic
formula for total energy E = mc2 to obtain
h = mc2
 = mc2/h
 The de Broglie wave velocity is therefore
vp =  = (mc2/h)(h/mv)
vp = c2/v
 As the particle velocity v must be less than the velocity of light c, the de Broglie
waves always travel faster than light.
Physical significance of y
 The physical significance of y
 According to Max Born | y | 2 does not give the particle density at any
point but gives the probability of finding the particle at the point at
any given momentum.
 The probability of finding a particle at a given point must be real, it is
taken as y*y or | y | 2 .
 More exactly, the probability of the particle being present in a volume
dx dy dz is | y | 2 dx dy dz.
 For the total probability of finding the particle somewhere is unity, i.e.
particle is certainly found somewhere in space:
∫ ∫ ∫ | y | 2 dx dy dz = 1
y satisfying this requirement is said to be normalized.
 Limitations on y
 We have seen that | y | 2 represent the probability density, the solution
that can be allowed for y from Schrödinger equation are subjected
to certain limitations. The most important limitations are:
 Y must be finite for all values of x,y,z
 Y must be single valued i.e for each set of a values of x,y.z, y must have one
value only.
 Y must be continuous in all regions except where potential energy is finite
 Y is analytical i.e. it possesses continuous first order derivative
 Y vanishes at the boundaries
 Orthogonal and normalized functions
 If the product of a function y1(x) and the complex conjugate y2*
(x) of a function y2 (x) vanishes, when integrated w.r.t x over the
interval a ≤ x ≤ b,
∫ab y2* (x) y1 (x) dx = 0
Then y1 and y2 are said to be mutually orthogonal in the interval
(a,b)
 Very often y is not normalized. W.k.t y could be multiplied by a
constant A, to give a new function Ay, which is also a solution of
wave-equation.
 To find a value of A such that the new wave function is a normalized
function
 For a normalized wave function it must satisfy the rquirement
∫ (Ay)* (Ay) dx dy dz = 1
| A | 2 ∫ y*y dx dy dz =1
| A | 2 =1 / ∫ y*y dx dy dz
| A | is known as normalizing constant