Photoelectric Effect

Basically, the photoelectric effect is the ejection

of electrons from a metal by shining light of a
particular frequency on it.
It doesn’t work for all wavelengths/frequencies
It was during 1887 that Hertz was conducting
the experiment in which the photoelectric effect
was discovered.
Light was shone onto the cathode, which at
certain frequencies emitted
electrons, which were
detected by the ammeter.
These emitted electrons
were called photoelectrons.
Named to show that light
was responsible for emitting
them.
The flow of these photoelectrons is called the
photocurrent.
In the initial set up of the experiment, the
cathode is made negative and the anode is made
positive.
When the photoelectrons are released from the
metal, they will naturally go to the positively
charged anode.
A sensitive ammeter will measure this
photocurrent flow
With this arrangement, the maximum current
flowing will be recorded by the ammeter.

All of the photoelectrons flowing across the gap

will have a certain amount of kinetic energy.
The amount depends on the location of the metal
that the electron came from
At or close to the surface – high energy
Well below the surface – low energy
When the anode and cathode had zero
potential, there was still a current being
recorded flowing across the gap.
Though not as high as when the anode was made
to be positive.
For electrons to be emitted, the light had to
have a certain frequency.
The minimum frequency that would cause this
is called the threshold or cut-off frequency, f0
Anything below this, would not provide enough
energy to eject electrons.
The German physicist Lenard found out the
following things:
The rate at which electrons are emitted depends on
the intensity of the light
High intensity – high current
Low intensity – low current
Cont’d..
Metals would only emit electron above certain
frequencies
Threshold frequency, f0

Electrons were emitted without any apparent time

delay
The time delay is actually about 10-9s

The intensity of light doesn’t affect the threshold

frequency.
Only frequency affects it
Lenard continued his investigations to find out
more about the kinetic energy of the electrons
being emitted.
In particular the maximum kinetic energy of the
released electrons

This was done by reversing the potential around

the circuit
The anode was made more and more negative
As this occurred, the current being recorded
was observed to decrease.

This showed that a decreasing number of

photoelectrons had enough energy to overcome
the opposing electric potential of the anode.

Electrons with little or no KE were stopped as soon

as the anode becomes negative
Once a certain potential was reached, no more
photoelectric current was recorded.

This point is called the stopping voltage, V0

The photoelectrons with the most KE being

stopped by Vo volts
Light with a higher frequency, was found to
have a higher stopping voltage.
Red light (low frequency)

No electrons emitted

i = 0A

Bright Red light

No electrons emitted

i = 0A
Green light. Electron emission starts

+ μA
e -
Small
current

Brighter Green light. Electron emission starts

μA
+ Bigger current
e -
Violet light. Electron emission continues

+
e- μA
Small current

Brighter Violet light. Electron emission continues

+ μA
e-
Bigger
current
 Dim Light
+

- e -
Small current

Small reversed voltage

Dim Light
-  +
e -


No current

More negative reversed voltage

 Hot plate.
A few electrons get
enough energy to just
barely “splash” out.

What is the current

vs battery voltage?
Current

Current
A B
0 Voltage
0 Voltage

Current
Current

D 0 Voltage
0 Voltage 17
 What’s happening here?
Each electron that pops out is accelerated more so hits
far plate with higher velocity,
BUT # of electrons = constant
sec
So current is constant!
Current

NOT V=IR !!

0 Battery Voltage
reverse V, Vacuum tube diode. Works.
no electrons - early electronic device.
flow. 18
Which graph represents low and high intensity curves?

I
I
A B

0 Batt. V 0 Batt. V

I
I

C D

0 Batt. V
0 Batt. V
I

0 Batt. V 19
 HIGH intensity LOW intensity

e’s

I
Fewer electrons pop off metal
Current decreases.
Current proportional to light intensity.
I
ans. B

0 Battery
20
Voltage
 Predict what happens to
the initial KE of the
electrons as the frequency
of light changes? (Light
intensity is constant)
e’s

I
Initial KE
Predict shape
of the graph

0 Frequency of light
21
 Initial KE

Initial KE
A B

0 Frequency 0 Frequency
Initial KE

Initial KE
C D

0 Frequency 0 Frequency

22
E. something different
Correct answer is D.
do sim showing graph

There is a minimum frequency

below which the light cannot
kick out electrons…
even if wait a long time
e’s

I
As the frequency of light increases
Initial KE

(shorter ), the KE of electrons

being popped off increases.
(it is a linear relationship)

0 Frequency of light 23
Summary of Photoelectric experiment results.
1. Current linearly proportional to intensity.
2. Current appears with no delay.
3. Electrons only emitted if frequency of light exceeds
a threshold. (same as “if wavelength short enough”).
4. Maximum energy that electrons come off with
increases linearly with frequency (=1/wavelength).
(Max. energy = -stopping potential)
5. Threshold frequency depends on type of metal.

24
 An analogy with a ball and a pit

Light like a Kicker…

Puts in energy. All concentrated
on one ball/electron. Ball emerges with:
Blue kicker always kicks the same, KE = kick energy - mgh
and harder than red kicker
mgh = energy needed to
always kicks.
make it up hill and out.
mgh for highest electron
analogous to work function.

h Kick energy. Top ones

get out, bottom don’t.
Harder kick (shorter
electrons
wavelength light),
metal more 25
get out.
Photon Energies:
Each photon has: Energy = Planks constant * Frequency
(Energy in Joules) (Energy in eV)
E=hf=(6.626*10-34 J-s)*(f s-1) E=hf= (4.14*10-15 eV-s)*(f s-1)
E=hc/ = (1.99*10-25 J-m)/( m) E= hc/1240 eV-nm)/(nm)

Red Photon: 650 nm Ephoton = 1240 eV-nm = 1.91 eV

650 nm
Work functions of metals (in eV):
Aluminum 4.08 eV Cesium 2.1 Lead 4.14 Potassium 2.3
Beryllium 5.0 eV Cobalt 5.0 Magnesium 3.68 Platinum 6.35
Cadmium 4.07 eV Copper 4.7 Mercury 4.5 Selenium 5.11
Calcium 2.9 Gold 5.1 Nickel 5.01 Silver 4.73
Carbon 4.81 Iron 4.5 Niobium 4.3 Sodium 2.28

26
Uranium 3.6
Zinc 4.3
The voltage at which the current is reduced to
zero, the ‘Stopping voltage’ Vo, gives a measure
of the maximum kinetic energy of the emitted
photoelectrons.
Ek max = ½mvmax2= eVo

e - Charge on an electron
V0 – stopping voltage
m – mass of an electron = 9.11 x 10-31kg
vmax – maximum speed of the electron
A photoelectron is released though doesn’t
make it to ‘the other side’ as the stopping
voltage is 6.0V.
What is the maximum kinetic energy of this
photoelectron and at what speed must it be
travelling?
If the stopping voltage is 6.0V, the maximum kinetic
energy must be 6.0eV
After further work by Philip Lenard between
1899 and 1902, Albert Einstein concluded that
light does in fact behave like a particle.

The wave model could not explain the

photoelectric effect.
 Compton Effect
When a monochromatic beam of X-rays is scattered from a
material then both the wavelength of primary radiation
(unmodified radiation) and the radiation of higher wavelength
(modified radiation) are found to be present in the scattered
radiation. Presence of modified radiation in scattered X-rays is
called Compton effect. E '  h '
h ' scattered
sin 
c photon
incident
E  h
photon 
 mv cos  h '
cos 
h electron c
p v
c
mv sin  recoiled electron
 From Theory of Relativity, total energy of the recoiled electron
with v ~ c is
E  mc 2  K  mo c 2
K  mc 2  mo c 2
mo c 2
K  mo c 2
1  v2 c2
 1 
K  mo c 2   1
 1  v 2 c 2 

Similarly, momentum of recoiled electron is

mo v
mv 
1  v2 c2
Now from Energy Conservation
 1 
h  h ' mo c 2   1 (i)
 1  v 2 c 2 
From Momentum Conservation
h h ' mo v
 cos   cos  (ii) along x-axis
c c 1  v2 c2
and

h ' mo v
0 sin   sin  (iii) along y-axis
c 1  v2 c2
Rearranging (ii) and squaring both sides
2
 h  h  '  m 2 2
ov
  cos    cos 
2
(iv)
 1 v c
2 2
 c c
Rearranging (iii) and squaring both sides
2
 h '
2 2
 m v
 sin    o
sin 2
 (v)
 1 v c
2 2
 c
Adding (iv) and (v)
2 2
 h    h  '  2 h 2
 ' m 2 2
ov
     cos   (vi)
 c   c  c 2
1  v 2
c 2

From equation (i)

h h ' mo c
  mo c 
c c 1  v2 c2
 On squaring, we get
2 2
 h   h '  2 h 2
 ' m 2 2
oc
     mo c 
2 2
 2hmo (  ' ) 
 c   c  c 2
1  v 2
c 2

(vii)
Subtracting (vi) from (vii)
2h 2 '
 2
(1  cos  )  2hmo (  ' )  0
c
2h 2 '
2hmo (  ' )  2
(1  cos  )
c
h '
mo (  ' )  2 (1  cos  )
c
 c c
But  and  ' So,
 '
1 1 h
mo c    (1  cos )
   '   '
  '  h
mo c  (1  cos  )
  '   '
h
 '    (1  cos  )
mo c
 is the Compton Shift.
It neither depends on the incident wavelength nor on the
scattering material. It depends only on the scattering angle i.e. 
h is called the Compton wavelength of the electron
mo c and its value is 0.0243 Å.
 Experimental Verification
photon Bragg’s X-ray
Monochromatic Spectrometer
X-ray Source
θ

Graphite
target

1. One peak is found at same

position. This is unmodified radiation
2. Other peak is found at higher
wavelength. This is modified signal of
low energy. 
3.  increases with increase in  .
 Compton effect difficult to observe in Visible Light

h
  (1  cos  )  0.0243 (1- cosθ) Å
mo c
 is maximum when (1- cosθ) is maximum i.e. 2.
max  0.05 Å
So Compton effect can be observed only for radiation having
wavelength of few Å.

For   1Å  ~ 1%
For   5000Å  ~ 0.001% (undetectable)
 Pair Production

Here a photon passes by a nucleus and converts

to a particle anti particle pair.
So what if a particle “decayed into
two similar mass particles?
 Pair Production

When a photon (electromagnetic energy) of sufficient energy

passes near the field of nucleus, it materializes into an electron
and positron. This phenomenon is known as pair production.

e

Photon
Nucleus (+ve) e

In this process charge, energy and momentum remains conserved

prior and after the production of pair.
 The rest mass energy of an electron or positron is 0.51 MeV
(according to E = mc2).

The minimum energy required for pair production is 1.02 MeV.

Any additional photon energy becomes the kinetic energy of the

electron and positron.
The corresponding maximum photon wavelength is 1.2 pm.
Electromagnetic waves with such wavelengths are called gamma
rays ( ).

Photon-nucleus pair production can only occur if the photons

have an energy exceeding twice the rest energy (mec2) of an
electron (1.022 MeV). These interactions were first observed in
Patrick Blackett's counter-controlled cloud chamber, leading to
the 1948 Nobel Prize in Physics.
 If hν > 2moc2 ≈ 1.02 MeV, the production of a pair of
electron and positron becomes possible close to a
charged massive object (eg. a nucleus) which takes
away the amount of momentum needed to preserve
momentum conservation during the interaction
with the Coloumb field of the massive object itself.

 The probability of pair production is a slowly

increasing function of energy while the Compton
probability decreases rapidly with increasing energy.
 Pair Annihilation
When an electron and positron interact with each other due to
their opposite charge, both the particle can annihilate
converting their mass into electromagnetic energy in the form of
two  - rays photon.

e  e    
Charge, energy and momentum are again conversed. Two
 - photons are produced (each of energy 0.51 MeV plus half
the K.E. of the particles) to conserve the momentum.
 The virtual particles must
recombine

You would never know it happens

….unless another particle “interferes” by changing the

momentum and energy of the system!
 Pair production cannot occur in empty space
From conservation of energy
h  2mo c 2

here mo is the rest mass and   1 1 v c 2 2

e
p
 p cos 
h c  p cos 
p
e
In the direction of motion of the photon, the momentum is
conserved if
h
 2 p cos 
c
 h  2cp cos  (i)
Momentum of electron and positron is
p  mo v
Equation (i) now becomes
h  2mo cv cos 
v
h  2mo c    cos 
2

c
But v 1 and cos   1
c
h  2mo c 2
But conservation of energy requires that

h  2mo c 2
Hence it is impossible for pair production to conserve both the
energy and momentum unless some other object is involved in
the process to carry away part of the initial photon momentum.
Therefore pair production cannot occur in empty space.
 Wave Particle Duality
Light can exhibit both kind of nature of waves and particles so the
light shows wave-particle dual nature.

In some cases like interference, diffraction and polarization it

behaves as wave while in other cases like photoelectric and
Compton effect it behaves as particles (photon).
 De Broglie Waves
Not only the light but every materialistic particle such as electron,
proton or even the heavier object exhibits wave-particle dual
nature.

De-Broglie proposed that a moving particle, whatever its nature,

has waves associated with it. These waves are called “matter
waves”.

Energy of a photon is
E  h
For a particle, say photon of mass, m

E  mc 2
 mc 2  hv
hc
mc 
2


h

mc
Suppose a particle of mass, m is moving with velocity, v then the
wavelength associated with it can be given by
h h
 or 
mv p
(i) If v  0    
means that waves are associated with moving
material particles only.
(ii) De-Broglie wave does not depend on whether the moving
particle is charged or uncharged. It means matter waves are not
electromagnetic in nature.
 Wave Velocity or Phase Velocity
When a monochromatic wave travels through a medium, its
velocity of advancement in the medium is called the wave
velocity or phase velocity (Vp).

Vp 
k
where   2
is the angular frequency

2
and k  is the wave number.

 Group Velocity
In practice, we came across pulses rather than monochromatic
waves. A pulse consists of a number of waves differing slightly
from one another in frequency.

The observed velocity is, however, the velocity with which the
maximum amplitude of the group advances in a medium.

So, the group velocity is the velocity with which the energy in the
group is transmitted (Vg).

The individual waves travel “inside” the group with their phase
velocities.
d
Vg 
dk
Relation between Phase and Group Velocity
d d
Vg   (kV p )
dk dk
dV p
Vg  V p  k
dk
2 dV p
Vg  V p 
 d 2  
1 dV p
Vg  V p 
 d 1  
 1dV p
Vg  V p 
 1 

 2 d  
  
dV p
Vg  V p  
d
In a Dispersive medium Vp depends on frequency

i.e.  constant
k
dV p
So,  is positive generally (not always).
d
 Vg  V p generally
 dV p
Vg  V p  
d

In a non-dispersive medium ( such as empty space)

  Vp
constant
k
dV p
 0
d
 Vg  V p
 Phase Velocity of De-Broglie’s waves
According to De-Broglie’s hypothesis of matter waves
h

mv
2 2mv
wave number k  (i)
 h
If a particle has energy E, then corresponding wave will have
frequency E

h
2E
then angular frequency will be   2 
h
 2mc 2
 (ii)
h
Dividing (ii) by (i)
 2mc 2 h
 
k h 2mv
c2
Vp 
v
But v is always < c (velocity of light)
(i) Velocity of De-Broglie’s waves V p (not
c acceptable)

(ii) De-Broglie’s waves (Vwill

p ) move faster than the particle
velocity (v) and hence the waves would left the particle
behind.
 Group Velocity of De-Broglie’s waves
The discrepancy is resolved by postulating that a moving particle
is associated with a “wave packet” or “wave group”, rather
than a single wave-train.
A wave group having wavelength λ is composed of a number of
component waves with slightly different wavelengths in the
neighborhood of λ.
Suppose a particle of rest mass mo moving with velocity v then
associated matter wave will have
2mc 2 and 2mv mo
 k where m
h h 1 v2 c2
 2mo c 2 2mo v
 and k
h 1 v c 2 2
h 1 v2 c2

On differentiating w.r.t. velocity, v

d 2mo v
 (i)
dv h1  v c  2
3
2 2

dk 2mo
 (ii)

dv h 1  v 2 c 2 3
2
 Dividing (i) by (ii)

d dv 2mo v
. 
dv dk 2mo

d
 v  Vg
dk
Wave group associated with a moving particle also moves with
the velocity of the particle.

Moving particle wave packet or wave group

Electron Microscope: Instrumental Application of
Matter Waves
 Resolving power of any optical instrument is proportional to
the wavelength of whatever (radiation or particle) is used to
illuminate the sample.

 An optical microscope uses visible light and gives 500x

magnification/200 nm resolution.

 Fast electron in electron microscope, however, have much

shorter wavelength than those of visible light and hence a
resolution of ~0.1 nm/magnification 1,000,000x can be
achieved in an Electron Microscope.
HRTEM Image of Ni Crystal
XRD Machine
 Particle Diffraction

Davisson & Germer experiment of electron diffraction

• If particles have a wave nature, then under appropriate

conditions, they should exhibit diffraction
• Davisson & Germer measured the wavelength of electrons
• This provided experimental confirmation of the matter waves
proposed by de Broglie
Davisson and Germer Experimental Setup
Incident Beam   90 0

 0
Current vs accelerating voltage has a maximum (a bump or
kink noticed in the graph), i.e. the highest number of electrons
is scattered in a specific direction.
The bump becomes most prominent for 54 V at φ ~ 50°
According to de Broglie, the wavelength associated with an electron
accelerated through V volts is
12.28 o
 A
V
Hence the wavelength for 54 V electron
12.28 o
  1.67 A
54
From X-ray analysis we know that the nickel crystal acts as a plane
diffraction grating with grating space d = 0.91 Å
From de Brogile's equation, we have

But since the kinetic energy of the electron

is equal to the energy gained from
accelerating through the electric potential,
 

Here the diffraction angle, φ ~ 50°

The angle of incidence relative to the family of Bragg’s plane
 180o  50o 
 
 
  65 o

 2 
From the Bragg’s equation
  2d sin 
o o
  2  (0.91 A)  sin 65  1.65 A
o

which is equivalent to the λ calculated by de-Broglie’s hypothesis.

It confirms the wavelike nature of electrons

Heisenberg Uncertainty Principle
Heisenberg Uncertainty Principle
Heisenberg Uncertainty Principle
Heisenberg Uncertainty Principle
 If x is measured accurately i.e. x  0  p x  
The principle applies to all canonically conjugate pairs of quantities in which
measurement of one quantity affects the capacity to measure the other.

Like, energy E and time t.


Et 
2
and angular momentum L and angular position θ

L 
2
In microscopic particles we can observe two type of
uncertainties viz.
Uncertainty in position and momentum
Uncertainty in energy and time

RESULTS OF UNCERTAINTY PRINCIPLE

It is impossible to chase an electron around the nucleus.
The principle describes the incompleteness of Bohr's atomic
theory.
According to Heisenberg's uncertainty principle there is no
circular orbit around the nucleus.
Exact position of an electron can not be determined precisely.

LIMITATIONS OF PRINCIPLE
Heisenberg's uncertainty principle is not applicable in our daily
life. It is only applicable on micro objects i.e. subatomic
particles.
 Determination of the position of a particle by a microscope
(Thought Experiment)
Suppose we want to determine accurately the position and momentum of
an electron along x-axis using an ideal microscope free from all mechanical
and optical defects.

The limit of resolution of the

microscope is

x 
2 sin i
here i is semi-vertex angle of the cone of
rays entering the objective lens of the
microscope. i
Scattered
x is the order of uncertainty in the x- Photon
component of the position of the Incident
electron. Photon Recoiled electron
 We can’t measure the momentum of the electron prior to illumination. So
there is uncertainty in the measurement of momentum of the electron.

The scattered photon can enter the microscope anywhere between the
angular range +i to –i.
The momentum of the scattered photon is (according to de-Broglie)
h
p

Its x-component can be given as
2h
p x  sin i

The x-component of the momentum of the recoiling electron has the same
uncertainty, p x
(conservation of momentum)
 The product of the uncertainties in the x-components of position and
momentum for the electron is
 2h
x.p x   sin i
2 sin i 

x.p x  h 
2
This is in agreement with the uncertainty relation.
 Applications of Heisenberg Uncertainty Principle

(i) Non-existence of electron in nucleus

Order of radius of an atom ~ 5 x10 -15 m

15
If electron exist in the nucleus then ( x ) max  5  10 m

xp x 
2

(x) max (p x ) min 
2

(p x ) min   1.110  20 kg.m.s 1
2x
then
E  pc  20MeV  relativistic
Thus the kinetic energy of an electron must be greater than 20
MeV to be a part of nucleus

Experiments show that the electrons emitted by certain unstable

nuclei don’t have energy greater than 3-4 MeV.

Thus we can conclude that the electrons cannot be present within

nuclei.
(ii) Concept of Bohr Orbit violates Uncertainty Principle

x.p 
2
p2
But E
2m

pp mvp x
E    p
m m t

E.t  x.p

E.t 
2
 According to the concept of Bohr orbit, energy of an electron in a orbit is
constant i.e. ΔE = 0.

E.t   t  
2
All energy states of the atom must have an infinite life-time.
But the excited states of the atom have life–time ~ 10-8 sec.
The finite life-time Δt gives a finite width (uncertainty) to the energy
levels.

(iii) Zero Point Energy

There cannot be a state in which the system sits motionless at the
bottom of its potential well. Therefore, the lowest-energy state (the
ground state) of the system must have a distribution in position and
momentum that satisfies the uncertainty principle, which implies its
energy must be greater than the minimum of the potential well (i.e.
zero energy).
 Two-slit Interference Experiment

Slit
1 meter

Laser
Slit Detector
Source

Rate of photon arrival = 2 x 106/sec

Rate of photon detection = 105/sec
Time lag = 0.5 x 10-6 sec
Spatial separation between photons = 0.5 x 10-6 c = 150 m
– Taylor’s experiment (1908): double slit experiment with very dim light:
interference pattern emerged after waiting for few weeks
– interference cannot be due to interaction between photons, i.e.
cannot be outcome of destructive or constructive combination of
photons
 interference pattern is due to some inherent property of each
photon - it “interferes with itself” while passing from source to
screen
– photons don’t “split” –
light detectors always show signals of
same intensity
– slits open alternatingly: get two overlapping single-slit diffraction
– patterns – no to
add detector two-slit interference
determine through which slit photon goes:
 no interference
– interference pattern only appears when experiment provides
no means of determining through which slit photon passes
 Double slit experiment – QM interpretation
– patterns on screen are result of distribution of photons
– no way of anticipating where particular photon will strike
– impossible to tell which path photon took – cannot assign specific
trajectory to photon
– cannot suppose that half went through one slit and half through other
– can only predict how photons will be distributed on screen (or over
detector(s))
– interference and diffraction are statistical phenomena associated with
probability that, in a given experimental setup, a photon will strike a
certain point
– high probability  bright fringes
– low probability  dark fringes
 Double slit expt. -- wave vs quantum
wave theory quantum theory

• pattern of fringes: • pattern of fringes:

– Intensity bands due to – Intensity bands due to
variations in square of variations in probability, P, of a
amplitude, A2, of resultant photon striking points on
wave on each point on screen screen
• role of the slits:
– to provide two coherent • role of the slits:
sources of the secondary – to present two potential
waves that interfere on the routes by which photon can
screen pass from source to screen
 Wave function
The quantity with which Quantum Mechanics is concerned is the wave
function of a body.
Wave function, ψ is a quantity associated with a moving particle. It is a
complex quantity.
|Ψ|2 is proportional to the probability of finding a particle at a
particular point at a particular time. It is the probability density.
|  |2   *
ψ is the probability amplitude.

Thus if   A  iB then  *  A  iB
|  |   *  A  i B  A  B
2 2 2 2 2 2
 Normalization
|Ψ|2 is the probability density.
The probability of finding the particle within an element of volume d
|  | d
2

Since the particle is definitely be somewhere, so



 d  1
 
2
| | Normalization


A wave function that obeys this equation is said to be normalized.

 Properties of wave function
1. It must be finite everywhere.
If ψ is infinite for a particular point, it mean an infinite large
probability of finding the particles at that point. This would
violates the uncertainty principle.
2. It must be single valued.
If ψ has more than one value at any point, it mean more than
one value of probability of finding the particle at that point
which is obviously ridiculous.

3. It must be continuous and have a continuous first derivative

everywhere.
  
, , must be continuous
x y z
4. It must be normalizable.
 Schrodinger’s time dependent wave equation
A basic physical principle that cannot be derived from anything else
Wave equation for a free particle moving in +x direction is
x
 i ( t  )
  Ae v

x
 2i (t  )
  Ae    2 v  c  

E  hv  2v
h 2
 
p p
i
( Et  px )
  Ae 
General form of wave equation for a free particle moving in +x direction is
i
( Et  px )
  Ae  (i)

where E is the total energy and p is the momentum of the particle

Differentiating (i) twice w.r.t. x
 2 p2  2

 2  p   
2 2
(ii)
x 2
 x 2

Differentiating (i) w.r.t. t

 iE 
   E  i (iii)
t  t
 For non-relativistic case
E = K.E. + Potential Energy

p2
E  V ( x, t )
2m
p2
 E    V (iv)
2m
Using (ii) and (iii) in (iv)
  2  2
i   V
t 2m x 2

This is the time dependent Schrodinger’s wave equation for a particle in

one dimension.
Schrodinger’s time independent wave equation
A basic physical principle that cannot be derived from anything else
Wave equation for a free particle moving in +x direction is
x
 i ( t  )
  Ae v

x
 2i (t  )
  Ae    2 v  c  

E  hv  2v
h 2
 
p p
i
( Et  px )
  Ae 
General form of wave equation for a free particle moving in +x direction is
i i i
( Et  px ) Et px
  Ae 
 Ae 
.e 

i
Et
   oe  (i)

where E is the total energy

Differentiating (i) twice w.r.t. x
 2  2 o  i Et
x 2 e
 (ii)
x 2

Differentiating (i) once w.r.t. t

 iE i
 Et
  o e  (iii)
t 
Substituting equations (ii) and (iii) in Schrodinger time dependent eqn.
as given below:

  2  2
i   V
t 2m x 2

 iE  Et 
i
 2
 2
 
i
Et 
i
Et
i    o e   

2 e
o   V o e  Using (i)
   2m x
So, first of all cancelling the common terms on both sides and then
rearranging of the terms leads to the below mentioned eqn.

 2 o 2mo
 2 ( E  V ) o  0
x 2

This is the time independent Schrodinger’s wave equation for a particle
in one dimension.
 As  ois function of x only so we can also write  (x)
 2 ( x) 2mo
 2 ( E  V ) ( x)  0
x 2

This is the time independent (steady state) Schrodinger’s wave equation
for a particle of mass mo, total energy E, potential energy V, moving
along the x-axis.

If the particle is moving in 3-dimensional space then we can write

 2  2  2 2mo
 2  2  2 ( E  V )  0
x 2
y z 
 Linearity and Superposition
If ψ1 and ψ2 are two solutions of any Schrodinger equation of a
system, then linear combination of ψ1 and ψ2 will also be a solution
of the equation..
  a1 1  a2 2 is also a solution
Here a1 & aare
2 constants

Above equation suggests:

(i) The linear property of Schrodinger equation
(ii) ψ1 and ψ2 follow the superposition principle
 If P1 is the probability density corresponding to ψ1 and P2 is the
probability density corresponding to ψ2
Then    1  2 due to superposition principle
Total probability will be
P |  |2 |  1   2 |2
 ( 1  2 )* ( 1  2 )
 ( 1*   2* )( 1  2 )
  1* 1  2* 2  1* 2   2* 1
P  P1  P2   1* 2   2* 1
P  P1  P2
Probability density can’t be added linearly
 Expectation values
Expectation value of any quantity which is a function of ‘x’ ,say f(x)
is given by 
 f (x)    f ( x) | | dx
2
for normalized ψ


Thus expectation value for position ‘x’ is



x   x | | dx
2


Expectation value is the value of ‘x’ we would obtain if we
measured the positions of a large number of particles described by
the same function at some instant ‘t’ and then averaged the
results.
 Q. Find the expectation value of position of a particle having wave
function ψ = ax between x = 0 & 1, ψ = 0 elsewhere.

Solution 1 1
 x    x |  |2 dx  a 2  x 3 dx
0 0

1
x  4
a  
2

 4 0
a2
x 
4
 Operators
(Another way of finding the expectation value)
An operator is a rule by means of which, from a given function we
can find another function.
For a free particle i
( Et  px )
  Ae 

Then
 i
 p
x 
Here
^  
p (i)
i x
is called the momentum operator
 Similarly  i
  E
t 
Here ^ 
E  i (ii)
t
is called the Total Energy operator

Equation (i) and (ii) are general results and their validity is the same as
that of the Schrodinger equation.
 If a particle is not free then
^
2
^ ^ ^ p
^ ^
E  K .E. U E U
2mo
2
 1    ^
i    U U  U
t 2m  i x 

 2 2
i   U
t 2m x 2

  2  2
i   U
t 2m x 2

This is the time dependent Schrodinger equation

 If Operator is Hamiltonian
^ 2 2
H  U
2m x 2

Then time dependent Schrodinger equation can be written as

^
H   E
This is time dependent Schrodinger equation in Hamiltonian form.
 Eigen values and Eigen function
Schrodinger equation can be solved for some specific values of energy i.e.
Energy Quantization.
The energy values for which Schrodinger equation can be solved are
called ‘Eigen values’ and the corresponding wave function are called
‘Eigen function’.
Suppose a wave function (ψ) is operated by an operator ‘α’ such that the
result is the product of a constant say ‘a’ and the wave function itself i.e.
^
   a
then ^
ψ is the eigen function of 
^
a is the eigen value of 
 d2
Q. Suppose   eis eigen function of operator
2x
then find
2
the eigen
value. dx
Solution. ^d2
G 2
dx
^ d 2 d 2 2x
G  2  2 (e )
dx dx
^
G   4e 2 x
^
G  4
The eigen value is 4.
 Particle in a Box
Consider a particle of rest mass mo enclosed in a one-dimensional box
(infinite potential well). V  V 
Boundary conditions for Potential
0 for 0 < x < L
V(x)= {  for 0 > x > L particle

Boundary conditions for ψ V 0

0 for x = 0
Ψ= { 0 for x = L x=0 x=L

Thus for a particle inside the box Schrodinger equation is

 2 2mo
 2 E  0 (i) V  0 inside
x 2

 h 2
  (k is the propagation constant)
p k
p 2mo E
k  
 
2mo E
k 2
(ii)
2
Equation (i) becomes
 2
 k 2
 0 (iii)
x 2

General solution of equation (iii) is

 ( x)  A sin kx  B cos kx (iv)

Boundary condition says ψ = 0 when x = 0

 (0)  A sin k .0  B cos k .0

0  0  B.1 B0
Equation (iv) reduces to
 ( x)  A sin kx (v)
Boundary condition says ψ = 0 when x = L

 ( L)  A sin k .L
0  A sin k .L
A  0  sin k .L  0
 sin k .L  sin n
 kL  n
n
k (vi)
L
Put this in Equation (v)
nx
 ( x)  A sin (vii)
L
When n # 0 i.e. n = 1, 2, 3…., this gives ψ = 0 everywhere.
Put value of k from (vi) in (ii)
2mo E
k 
2

2
2
 n  2mo E
   2
 L  
  k 2 2
n2h2
E  2
(viii)
2mo 8mo L
Where n = 1, 2, 3….
Equation (vii) concludes
1. Energy of the particle inside the box can’t be equal to zero.
The minimum energy of the particle is obtained for n = 1
h2
E1  (Zero Point Energy)
8mo L2
If E1  0momentum i.e.
0 p  0
 x  
But xmax  the
since L particle is confined in the box of dimension L.
 Thus zero value of zero point energy violates the Heisenberg’s
uncertainty principle and hence zero value is not acceptable.

2. All the energy values are not possible for a particle in

potential well.
Energy is Quantized
3. En are the eigen values and ‘n’ is the quantum number.
4. Energy levels (En) are not equally spaced.
n=3 E3
n=2 E2
n=1
E1
Eigen Function: Again starting with eqn. (vii)
nx
 n ( x)  A sin
L
Using Normalization condition


 n dx  1
2
| ( x ) |


nx
L
A  sin
2 2
dx  1
0
L
L 2
A   1  A 
2

2 L
The normalized eigen function of the particle are
2 nx
 n ( x)  sin
L L
Probability density figure suggest that:
1. There are some positions (nodes) in the box that will never be
occupied by the particle.
2. For different energy levels the points of maximum probability are
found at different positions in the box.
|ψ1|2 is maximum at L/2 (middle of the box)
|ψ2|2 is zero L/2.
 Particle in a Three Dimensional Box

Eigen energy E  Ex  E y  Ez
2
h
E  (nx2  n y2  nz2 )
8mL2
Eigen function    x y z

nxx n yy nzz

  Ax Ay Az sin sin sin
L L L
3
 2 nxx n yy nzz

   sin sin sin
L  L L L
 