Physics

(PHY211C)
BTECH - 1st Semester

Quantum Mechanics

Dr Akhilesh Tiwari, Associate Professor, IIIT Allahabad

 -: Syllabus :-
Unit 2:-Basic ideas of Quantum Mechanics:- (8)

Matter Waves; Wave and Group Velocities, Heisenberg

Uncertainty Principle, Wave Function, its Interpretation and
Normalization; Superposition of Amplitudes, Dynamical Variables
as Operators; Expectation Values; Schrodinger Equation and its
Simple Applications like Particle in a Box, Quantum Well,
Potential Barrier Problem.
 Classical Mechanics Quantum Mechanics

(Newton: 1642-1727) (Bohr, Heisenberg,

Schrodinger, et al.)

Special Relativity Quantum Field Theory

(Einstein. 1905 was a big (Dirac, Pauli, Feynman,

year.) Schwinger, et al.)

The Four Forces to Which Mechanics is Applied:

1. Strong
2. Electromagnetic
3. Weak
4. Gravitational
 Basics of Quantum Mechanics
Wave properties of Particles:

“Quantum” means BUNDLE in Latin.

Therefore, we are going to study the motion of objects that

travel in small bundles called as Quanta. These tiny
bundles of energy were called Photons, and behave almost
exactly like a material particle.
 The Birth of Quantum Mechanics
___________________________
• At the turn of the last century, 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 led to the development of Quantum

Mechanics which is today regarded as the
fundamental theory of Nature.
 Some key events/observations that led to the
development of quantum mechanics…
_________________________________
• Black body radiation spectrum (Planck, 1901)
Planck
• Photoelectric effect (Einstein, 1905)
Einstein
• Model of the atom (Rutherford, 1911)
• Quantum Theory of Spectra (Bohr, 1913)
Rutherford

Bohr
 Few more…
_________________________________
Compton

• Scattering of photons off electrons (Compton, 1922)

• Exclusion Principle (Pauli, 1922)

Pauli

• Matter Waves (de Broglie 1925)

de Broglie

• Experimental test of matter waves (Davisson and

Germer, 1927)

Davisson and Germer

Matter Waves and the Uncertainty
Principle
_________________________
 The story of light…
_______________________________

• Corpuscular theory (Newton)

• Wave nature (Huygens)

• Double-slit interference experiment (Young)

 The story of light (contd.)…
_______________________________
• Light is an electromagnetic wave (Maxwell)
• Photoelectric effect – existence of light quanta
– photons (Einstein)
• Photons have momentum (Compton)…
EM Wave Spectrum
Visible Spectrum
 The nature of light…
____________________________
• The birth of quantum mechanics is intimately
linked with the theories and discoveries
relating to the nature of light

• Is the nature of light that of a wave or a

particle ?
 Light has a dual nature
___________________________
• Wave (electromagnetic) - Interference
- Diffraction

• Particle (photons) - Photoelectric effect

- Compton effect

Wave - Particle Duality for light

 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!
Matter Waves
Matter waves or de Broglie waves
Energy of photon can written as
(since c =  )
Where, h is Planck’s constant, c velocity of light,  is frequency and  is the
wavelength.
If photon possesses some mass by virtue of its motion (because its rest mass is
zero). According to theory of relativity
E (Energy) = m (mass of photon) c2
Hence
De Broglie wave continued…

This equation represents wavelength  of the

wave associated with a moving material
particle having a momentum mv.

Velocity of de Broglie waves:

De Broglie wave continued…

As we know

Then

de Broglie wave velocity

2
c
(v p ) 
v
 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
The connecting link – Planck’s constant
_______________________________
Dual Nature

Radiation E  h
h
Matter 
p
Why isn’t the wave nature of matter more
apparent to us…?
___________________________________

 34
h  6 . 626068 x10 J.s
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!
 Particle
______________________________

Our traditional understanding of a particle…

“Localized” - definite position, momentum,

confined in space
 Wave
____________________________
Our traditional understanding of a wave…

“de-localized” – spread out in space and time

How do we associate a wave nature to a
particle?
___________________________________
What could represent both wave and particle?

• Find a description of a particle which is

consistent with our notion of both particles
and waves…
•
• Fits the “wave” description

• “Localized” in space
 A “Wave Packet”
____________________________________

How do you construct a wave packet?

 What happens when you add up waves?
________________________________
The Superposition principle
Adding up waves of different frequencies…
____________________________________
Constructing a wave packet by adding up several
waves …
___________________________________
If several waves of different wavelengths
(frequencies) and phases are superposed
together, one would get a resultant which
is a localized wave packet
 A wave packet describes a particle
____________________________

• A wave packet is a group of waves with slightly

different wavelengths interfering with one another in
a way that the amplitude of the group (envelope) is
non-zero only in the neighbourhood of the particle

• A wave packet is localized – a good representation for

a particle!
 Wave packet, phase velocity and group velocity
____________________________

• The spread of wave packet in wavelength depends on

the required degree of localization in space – the
central wavelength is given by
h
 
p
• What is the velocity of the wave packet?
 Wave packet, phase velocity and group velocity
________________________________

• The velocities of the individual waves which superpose

to produce the wave packet representing the particle are
different - the wave packet as a whole has a different
velocity from the waves that comprise it
• Phase velocity: The rate at which the phase of the wave
propagates in space
• Group velocity: The rate at which the envelope of the
wave packet propagates
 Wave packet, phase velocity and group velocity
________________________________

2
Phase velocity c
vp 
v

Group velocity vg  v

Here c is the velocity of light and v is the velocity

of the particle
 Are matter waves for real?!
__________________________________
 Today, advances in technology have led to
matter wave interference experiments being
demonstrated successfully not only with
electrons but neutrons, atoms, and big and
small molecules!

 Infact, the largest molecule showing

interference has almost a 100 atoms!
 Are matter waves for real?!
__________________________________

 C60 molecules (Fullerenes or Bucky Balls) have a wave

nature! (A. Zeilinger et al, Vienna, 1999)

 Biomolecules have it too!

 Porphyrin
(2003)
 Are matter waves for real?!
__________________________________

What next? – Matter wave interference for a

Virus?!
 Matter waves are real….
_______________________________

If there is wave, there must be a wave

equation………

The Schrödinger Equation

 Wave Function ()
_______________________________
 Wave Function (Born Interpretation)
__________________________________
 In matter waves, the quantity that refers to the
propagation of wave is called wave function
and is denoted by 
. psi.

 The values of the wave function associated

with a moving particle at some point (x, y, z) in
space at time t is related to the probability of
finding the body at that point at time t.

 It has no physical interpretation.

Properties of Valid Wave Functions
Boundary conditions
1) In order to avoid infinite probabilities, the wave function must be finite
everywhere.
2) In order to avoid multiple values of the probability, the wave function must be
single valued.
3) For finite potentials, the wave function and its derivative must be continuous.
This is required because the second-order derivative term in the wave
equation must be single valued. (There are exceptions to this rule when V is
infinite.)
4) In order to normalize the wave functions, they must approach zero as x
approaches infinity.

• Solutions that do not satisfy these properties do not generally

correspond to physically realizable circumstances.

40
The Born interpretation of the Wave Function

• The Wave function

– Contains all the dynamic information
about the system
– Born made analogy with the wave theory
of light (square of the amplitude is
interpreted as intensity – finding
probability of photons)
– Probability to find a particle is
proportional to  2   * Probability Density

– It is OK to have negative values for wave

Max Born
function
Born interpretation of the Wave Function
Born interpretation of the Wave Function
Heisenberg’s Uncertainty Principle
_________________________
Heisenberg’s Uncertainty Principle

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
 Role of an Observer in Quantum Mechanics

• The observer is not objective and passive

• The act of observation changes the physical

system irrevocably

• This is known as subjective reality

 Heisenberg realized 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
 Measuring the position and momentum
of an electron (cont’d)…
• By Planck’s law E = hc/, a photon with a short
wavelength has a large energy

• Thus, it would impart a large ‘kick’ to the

electron

• But to determine its momentum accurately,

electron must only be given a small kick

• This means using light of long wavelength!

 Fundamentals…
• Use light with short wavelength:

– accurate measurement of position but not momentum

• Use light with long wavelength:

– accurate measurement of momentum but not position

 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
 Example of Tennis Ball
• A player throws a 100 g baseball at 40 m/s

• So momentum is 0.1 x 40 = 4 kg m/s

• Suppose the momentum is measured to an

accuracy of 1 percent , i.e.,

Dp = 0.01 p = 4 x 10-2 kg m/s

 Example … (cont’d)
• The uncertainty in position is then

• No wonder one does not observe the effects

of the uncertainty principle in everyday life!
 Example of Electron
• Same situation, but baseball replaced by an
electron which has mass 9.11 x 10-31 kg

• So momentum = 3.6 x 10-29 kg m/s

and its uncertainty = 3.6 x 10-31 kg m/s

• The uncertainty in position is then

 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

• The energy can be known with perfect

precision (DE = 0), only if the measurement is
made over an infinite period of time (Dt = ∞)
 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's Uncertainty Principle
__________________________________

Uncertainty in Position : Dx

Uncertainty in Momentum: Dp x

h
D xD p x 
4
 Heisenberg's Uncertainty Principle
- applies to all “conjugate variables”
___________________________________

Position & momentum h

D xD p x 
4

h
Energy & time
DEDt 
4
Uncertainty Principle and the Wave Packet
___________________________________
h h D  Dp
D xD p   
x
4 p  p

Dx

If Dp is large, Dx is small

Dx
 Some consequences of the Uncertainty Principle
___________________________________

• The path of a particle (trajectory) is not well-defined in

quantum mechanics

 Electrons cannot exist inside a nucleus

 Atomic oscillators possess a certain amount of energy

known as the zero-point energy, even at absolute zero.
Why isn’t the uncertainty principle apparent to
us in our ordinary experience…?
Planck’s constant, again!!
___________________________________
h h  6 .63 x10  34
J.s
D xD p x 
4
Planck’s constant is so small that the
uncertainties implied by the principle are also
too small to be observed. They are only
significant in the domain of microscopic
systems
 Summary: Lessons from Heisenberg
• The idea of a perfectly predictable universe
cannot be true

• There is no such thing as an ideal, objective

observer
Normalization
____________________
 Normalization

• When ψ is a solution, so is Nψ
• We can always find a normalization const. such that the
proportionality of Born becomes equality

  dx  1
 Normalization const. are
*
already contained in wave
  *
 dxdydz    d  1
 * function
 Probability Density

B=0

2 2
  Ae ikx
  A

A=0

2 2
  Be  ikx
 B

A=B
2 2
  2 Acos kx   4 A cos 2
kx
nodes
 Schrödinger equation

• 1926, Erwin Schrödinger (Austria)

– Describe a particle with wave function
– Wave function has full information about the
particle

Time independent Schrödinger equation

for a particle in one dimension
Schrodinger Equation
General form

H = E 
H= T + V
: Hamiltonian
operator
The Schrodinger equation:

Kinetic + Potential Total

=
energy energy energy

For a given U(x),

• what are the possible (x)?
• What are the corresponding E?
For a free particle, U(x) = 0, so

2 2
 (x)  Ae ikx k
E
 2m
Where k = 2
= anything real = any value from
0 to infinity

The free particle can be found anywhere, with

equal probability
 Quantization

• Energy of a particle is
quantized
 Acceptable energy can be found
by solving Schrödinger equation

 There are certain limitation in

energies of particles
 The information in a wave function

• Simple case
– One dimensional motion, V=0

 2 d 2
 2
 E
2m dx
Solution

k 2 2
  Aeikx  Be  ikx E
2m
 Operators

̂  
• Position x x̂  x 

• Momentum px pˆ x 
 d
i dx

• Potential energy 1 2
V  kx ˆ 1 2
V  kx 
2 2

• Kinetic energy EK 
p x2  2
d 2
Eˆ K  
2m 2m dx 2
• Total energy Hˆ  Eˆ K  Vˆ  
 2
d 2
 Vˆ
2m dx 2
 Eigen values and eigen fucntions

• Eigenvalue equation

(Operator)(function) = (constant factor)*(same function)

̂  
Operator

Eigenfunction Eigenvalue

Solution : Wave function Allowed energy (quantization)

(operator corresponding to observable)  (value of observable) 

Time-Independent Schrödinger Wave
Equation
• The potential in many cases will not depend explicitly on time.
• The dependence on time and position can then be separated in the
Schrödinger wave equation. Let ,

which yields:

Now divide by the wave function:

• The left side of Equation () depends only on time, and the right side depends
only on spatial coordinates. Hence each side must be equal to a constant. The
time dependent side is

74
Time-Independent Schrödinger Wave
Equation Continued
 We integrate both sides and find:

where C is an integration constant that we may choose to be 0. Therefore

This determines f to be

 This is known as the time-independent Schrödinger wave equation, and it is a

fundamental equation in quantum mechanics.

75
Stationary State

• The wave function can be written as:

• The probability density becomes:

• The probability distributions are constant in time. This is a standing wave

phenomena that is called the stationary state.

76
Comparison of Classical and Quantum
Mechanics
 Newton’s second law and Schrödinger’s wave equation are
both differential equations.
 Newton’s second law can be derived from the Schrödinger
wave equation, so the latter is the more fundamental.
 Classical mechanics only appears to be more precise because
it deals with macroscopic phenomena. The underlying
uncertainties in macroscopic measurements are just too small
to be significant.

77
Expectation Values
• The expectation value is the expected result of the average of many
measurements of a given quantity. The expectation value of x is
denoted by <x>
• Any measurable quantity for which we can calculate the expectation
value is called a physical observable. The expectation values of
physical observables (for example, position, linear momentum,
angular momentum, and energy) must be real, because the
experimental results of measurements are real.
• The average value of x is
Continuous Expectation Values

• We can change from discrete to

continuous variables by using the
probability P(x,t) of observing the
particle at a particular x.

• Using the wave function, the

expectation value is:

• The expectation value of any function

g(x) for a normalized wave function:
Momentum Operator
• To find the expectation value of p, we first need to represent p in terms of x
and t. Consider the derivative of the wave function of a free particle with
respect to x:

With k = p / ħ we have

This yields

• This suggests we define the momentum operator as .

• The expectation value of the momentum is

Position and Energy Operators
 The position x is its own operator as seen above.
 The time derivative of the free-particle wave function is

Substituting ω = E / ħ yields

 The energy operator is

 The expectation value of the energy is

81
Infinite Square-Well Potential
• The simplest such system is that of a particle trapped in a box with
infinitely hard walls that the particle cannot penetrate. This potential is
called an infinite square well and is given by

• Clearly the wave function must be zero where the potential is infinite.

• Where the potential is zero inside the box, the Schrödinger wave

equation becomes where .

• The general solution is .

Quantization
• Boundary conditions of the potential dictate that the wave function must be
zero at x = 0 and x = L. This yields valid solutions for integer values of n such
that kL = nπ.

• The wave function is now

• We normalize the wave function

• The normalized wave function becomes

• These functions are identical to those obtained for a vibrating string with fixed
ends.
Quantized Energy
• The quantized wave number now becomes
• Solving for the energy yields

• Note that the energy depends on the integer values of n. Hence the
energy is quantized and nonzero.
• The special case of n = 0 is called the ground state energy.
Finite Square-Well Potential

• The finite square-well potential is

• The Schrödinger equation outside the finite well in regions I and III is
or using

yields . Considering that the wave function must be zero at

infinity, the solutions for this equation are
 Finite Square-Well Solution
• Inside the square well, where the potential V is zero, the wave equation
becomes where

• Instead of a sinusoidal solution we have

• The boundary conditions require that

and the wave function must be smooth where the regions meet.

• Note that the

wave function is
nonzero outside
of the box.

86
Penetration Depth

• The penetration depth is the distance outside the potential well where the
probability significantly decreases. It is given by

• It should not be surprising to find that the penetration distance that violates
classical physics is proportional to Planck’s constant.

87
 Three-Dimensional Infinite-Potential Well
• The wave function must be a function of all three spatial coordinates. We
begin with the conservation of energy
• Multiply this by the wave function to get

• Now consider momentum as an operator acting on the wave function. In

this case, the operator must act twice on each dimension. Given:

• The three dimensional Schrödinger wave equation is

88
 Degeneracy
• Analysis of the Schrödinger wave equation in three dimensions introduces
three quantum numbers that quantize the energy.

• A quantum state is degenerate when there is more than one wave function
for a given energy.

• Degeneracy results from particular properties of the potential energy

function that describes the system. A perturbation of the potential energy
can remove the degeneracy.

89
 Simple Harmonic Oscillator
• Simple harmonic oscillators describe many physical situations: springs, diatomic
molecules and atomic lattices.

• Consider the Taylor expansion of a potential function:

Redefining the minimum potential and the zero potential, we have

Substituting this into the wave equation:

Let and which yields .

90
Parabolic Potential Well

• If the lowest energy level is zero, this violates the uncertainty principle.
• The wave function solutions are where Hn(x) are Hermite
polynomials of order n.

• In contrast to the particle in a box, where the oscillatory wave function is a sinusoidal
curve, in this case the oscillatory behavior is due to the polynomial, which dominates at
small x. The exponential tail is provided by the Gaussian function, which dominates at
large x.

91
Analysis of the Parabolic Potential Well

• The energy levels are given by

• The zero point energy is called the Heisenberg limit:

• Classically, the probability of finding the mass is greatest

at the ends of motion and smallest at the center (that is,
proportional to the amount of time the mass spends at
each position).
• Contrary to the classical one, the largest probability for
this lowest energy state is for the particle to be at the
center.

92
Barriers and Tunneling
• Consider a particle of energy E approaching a potential barrier of height V0 and the
potential everywhere else is zero.
• We will first consider the case when the energy is greater than the potential barrier.
• In regions I and III the wave numbers are:

• In the barrier region we have

93
Reflection and Transmission
• The wave function will consist of an incident wave, a reflected wave, and a
transmitted wave.
• The potentials and the Schrödinger wave equation for the three regions are as
follows:

• The corresponding solutions are:

• As the wave moves from left to right, we can simplify the wave functions to:

94
Probability of Reflection and Transmission
• The probability of the particles being reflected R or transmitted T is:

• The maximum kinetic energy of the photoelectrons depends on the value of

the light frequency f and not on the intensity.
• Because the particles must be either reflected or transmitted we have: R + T =
1.
• By applying the boundary conditions x → ±∞, x = 0, and x = L, we arrive at the
transmission probability:

• Notice that there is a situation in which the transmission probability is 1.

95
Tunneling
• Now we consider the situation where classically the particle does not have enough
energy to surmount the potential barrier, E < V0.

• The quantum mechanical result, however, is one of the most remarkable features of
modern physics, and there is ample experimental proof of its existence. There is a small,
but finite, probability that the particle can penetrate the barrier and even emerge on the
other side.
• The wave function in region II becomes

• The transmission probability that

describes the phenomenon of tunneling is

96
Uncertainty Explanation
• Consider when κL >> 1 then the transmission probability becomes:

• This violation allowed by the uncertainty principle is equal to the negative

kinetic energy required! The particle is allowed by quantum mechanics and
the uncertainty principle to penetrate into a classically forbidden region. The
minimum such kinetic energy is:

97
Analogy with Wave Optics
• If light passing through a glass prism reflects from an
internal surface with an angle greater than the critical
angle, total internal reflection occurs. However, the
electromagnetic field is not exactly zero just outside the
prism. If we bring another prism very close to the first one,
experiments show that the electromagnetic wave (light)
appears in the second prism The situation is analogous to
the tunneling described here. This effect was observed by
Newton and can be demonstrated with two prisms and a
laser. The intensity of the second light beam decreases
exponentially as the distance between the two prisms
increases.

98
Potential Well

• Consider a particle passing through a potential well region rather than through a potential
barrier.
• Classically, the particle would speed up passing the well region, because K = mv2 / 2 = E + V0.

According to quantum mechanics, reflection and transmission may occur, but the wavelength
inside the potential well is smaller than outside. When the width of the potential well is
precisely equal to half-integral or integral units of the wavelength, the reflected waves may be
out of phase or in phase with the original wave, and cancellations or resonances may occur.
The reflection/cancellation effects can lead to almost pure transmission or pure reflection for
certain wavelengths. For example, at the second boundary (x = L) for a wave passing to the
right, the wave may reflect and be out of phase with the incident wave. The effect would be a
cancellation inside the well.

99
Alpha-Particle Decay
• The phenomenon of tunneling explains the alpha-particle decay of heavy,
radioactive nuclei.
• Inside the nucleus, an alpha particle feels the strong, short-range attractive nuclear
force as well as the repulsive Coulomb force.
• The nuclear force dominates inside the nuclear radius where the potential is
approximately a square well.
• The Coulomb force dominates
outside the nuclear radius.
• The potential barrier at the nuclear
radius is several times greater than
the energy of an alpha particle.
• According to quantum mechanics,
however, the alpha particle can
“tunnel” through the barrier. Hence
this is observed as radioactive decay.

100
 Summary
___________________________________
 Matter and radiation have a dual nature – of
both wave and particle

 The matter wave associated with a particle has a

de Broglie wavelength given by

h

p
 Summary (contd.)
___________________________________

 A (localized) particle can be represented by a group of

waves called a wave packet

 The group velocity of the wave packet is vg  v

c2
 The phase velocity of the wave packet is v p 
v
 Summary (contd.)
___________________________________
 Heisenberg’s uncertainty principle is an important
consequence of the wave-particle duality of matter and
radiation and is inherent to the quantum description of
nature

 It applies to all conjugate variables and also to the

notion of the wave packet
h h
D xD p x  DEDt 
4 4
 Are matter waves for real?!
__________________________________
 In 1927 Davisson and Germer showed that electrons can
diffract – they act like waves

 Big application – Electron Microscopes

 Are matter waves for real?!
__________________________________
Double –slit experiment with electrons (1989)
(www.hqrd.hitachi.co.jp/em/doubleslit.cfm)