QUANTUM MECHANICS

1
 Course outline…

Quantum Mechanics: Wave equation, Time

dependent Schrodinger equation, Linearity &
superposition, Expectation values, Observables as
operators, Stationary states and time evolution of
stationary states, Eigenvalues & Eigenfunctions, Boundary
conditions on wave function, Application of SE (Particle in
a box, Potential barrier and step, one dimensional
harmonic oscillator)

References:
A. Beiser, Concept of Modern Physics (or Perspective of Modern
Physics), Tata-McGraw Hill, 2005.
D. J. Griffith, Introduction to Quantum Mechanics, Pearson, 2007.

2
 Quantum Mechanics

The methods of Quantum Mechanics

consist in finding the wave function
associated with a particle or a system

“everything” about the system!

3
HOWEVER
Since the wavefunction, Ψ(x,t), describes a particle,
its evolution in time under the action of the wave
equation describes the future history of the
particle

Ψ(x,t) is determined by Ψ(x, t = 0)

Thus, instead of the coordinate and velocity at t = 0

we want to know the wave function at t = 0

Thus uncertainty is built in from the beginning

4
 EM Waves in Empty Space
Maxwell’s equations:
partial derivatives for the fields in empty space:
 2E  2E  2B  2B
 μoεo 2 and  μoεo 2
x 2
t x 2
t

simplest solution: a sinusoidal wave:

E = Emax sin (kx – ωt), B = Bmax sin (kx – ωt)
wave number: k = 2π/ λ (λ is the wavelength)
angular frequency: ω = 2πƒ (ƒ =1/t is the wave frequency)

1
vc  2.99792 108 m / s
0 0
5
 Classical Wave Operators
Consider the wave equation for light

 2 E ( x, t ) 1  2 E ( x, t )
 2
x 2
v t 2

For a traveling wave solutions are the eigenvectors,

sin(kx-t), and eigenvalues of the operator on the
left hand side are -k2

For a standing wave between two reflecting mirros

separated by a distance a, the eigenvalues are, -kn2 =
n22/a2

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 Foundations of Quantum Mechanics
The wave function of a system evolves in time: time-dependent
Schrödinger equation:
  x, t   2  
i    U  x    x, t 
t  2 m x 2

Any measurement of the observable a corresponds to
operator Â, the only values that will ever be observed are
the eigenvalues of Â, which satisfy the eigenvalue
equation
Aˆ   x, t   A   x, t 

If a system is in a state described by a wave function  (x,t),

then the average value of the observable a (measured once on
many identical systems) is given by


   x, t  Aˆ   x, t  dx
*

a  


   x, t    x, t  dx
*


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 Conditions on 
The  must:

1. be a continuous and single-valued function of all x

and t (the probability density must be uniquely defined)

2. have a continuous first derivative (the exception -

points where the potential is infinite)

3. Have a finite normalization integral (so we can

define a normalized probability)

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 Normalization
The probability of finding a particle somewhere in space
must be unity, thus the normalization condition:
   r , t  d 3r  1
2

all space
In 1D:

- a wavefunction which obeys this condition
   x, t  dx  1 is said to be normalized
2

Suppose we have a solution to the Sch. Eq. that is not

normalized. The recipe for normalization:


 Calculate the normalization integral N   ( x, t ) dx

2


1
 Re-scale the wave function as  'r , t    r ,t 
N
This procedure works because any solution of the S.Eq. being
multiplied by a constant remains a solution: the S..Eq. is linear
and homogeneous.
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 Quantum Mechanical Operators
Physical Quantity  Operators
symbol  actual operation

 
Momentum p x  pˆ x 
i x
ˆ 
Total Energy E  E  i
t
Coordinate x  xˆ  x
Potential Energy U ( x)  Uˆ ( x)  U ( x)
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 Wave Function of Free Particle
Since the de Broglie expression is true for any
particle, we assume that free particles can be
described by a traveling wave, i.e. the
wavefunction of a free particle is a traveling
wave
For classical waves:
A cos[ kx  t ], A sin[ kx  t ]
However, these functions are not eigen functions of the
momentum operator, with them we do not find
But let’s try operating on the following wave function with ,
  h 2 h
pˆ x    k      p  p x 
i x 2  
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 Get same result of course if operate on

( x, t )  Acos[kx  t ]  i sin[ kx  t ]  A exp(ikx  t )

  i ( kx t ) 
pˆ x  ( x, t )  Ae  ikAei ( kx t )  kAei ( kx t )  k ( x, t )
i x i

Similarly can operate on  ( x, t )  A exp( ikx  t )

with ˆ 
E  i
t

Eˆ  x, t   i Aei ( kx t )  i(i ) Aei ( kx t )  Aei ( kx t )  E x, t 
t

This wave function is an eigenfunction of both momentum and energy

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 Expectation Values
Only average values of physical quantities can be determined
(can’t determine value of a quantity at a point)
These average values are called Expectation Values

These are values of physical quantities that quantum mechanics predicts

and which, from experimental point of view, are averages of multiple
measurements

Example, [expected] position of the particle

 
x  

xP( x)dx , with 

P( x)dx  1

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 Expectation Values
Since P(r,t)dV=|Ψ(r,t)|2dV, we have a way to
calculate expectation values if the wavefunction for
the system (or particle) is known
 

 
2 2
x  xP( x , t )dx  x ( x , t ) dx , since ( x , t )   * ( x , t )( x , t )
 

x  

 * ( x , t )x( x , t )dx

In general for a Physical Quantity W

Below Ŵ is an operator acting on wavefunction Ψ(r,t)

 

W  

ˆ ( x , t ) dx
 * ( x, t) W

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 Expectation Value
for Momentum of a Free Particle
 
*    
p   ( x)  p ( x)dx   ( x)   i  ( x) dx
ˆ *

   x  
Generally 
 ( x)
p  i  ( x)  dx *


x

 
 ( x)  Aeikx with   ( x) dx   Ae  Ae dx  1,
2 ikx * ikx

 

where A  0 as limits of integratio n  


Free Particle p   Ae   
ikx *
 i x Ae
ikx 
 dx
  
 

 Ae      Ae dx  k  p


ikx *
ik Aeikx dx  k  Aeikx
*
p  ikx


i 
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 Properties of the Wavefunction and its First
Derivative

1. must be finite for all x

2. must be single-valued for all x
3. must be continuous for all x
 
  
U ( x)   ( x)U ( x) ( x)dx 
  ( x)  i  ( x)dx
* *
px
 x 
 


 
E   ( x, t ) i  ( x, t )dx
*

  t 
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 Schrödinger Equation
Schrödinger developed the wave equation which can be solved to find the
wavefunction by translating the equation for energy of classical physics into the
language of waves

p2  2  2 x  
 U ( x)  E   U ( x) x   i  x 
2m 2m  x 2
t
For fixed energy, we obtain the time-independent Schrödinger equation, which
describes stationary states
 2  2 x 
  U ( x) x   E x 
2m  x 2

Energy of such states does not change with time ψn(x)

is an eigen function or eigen state U is a potential
function representing the particle interaction with the
environment
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 Stationary state

Assume V is independent of t , use separation of

variables

Deduce from equation (2.1) , then

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 ...(2.2)

time-independent Schrödinger
equation

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 Properties of 
Wave functions add, not the probabilities
(i) Linearity and superposition
Linearity: An important properties of Schrodinger equation: it is linear in the ,
the equation has terms that contain  and its derivatives but no terms independent
of  or that involve higher powers of  or its derivatives.
Superposition: If 1 and 2 are two solutions,
 = a11 + a22 is also a solution; 1 and 2 obey the superposition principle.
Interference effects can occur for wave functions just as they can for light, sound, etc
Superposition's to the diffraction of an electron beam:
Slit 1 is open: probability density: P1 = I1I2 = 1* 1

Slit 2 is open: probability density: P2 = I2I2 = 2* 2

Both open, probability density at screen:

P = II2 = I1+ 2I2 = (1* + 2*)( 1+ 2)

=  1* 1 + 2* 2 + 1* 2 + 2* 1

= P1+ P2+ 1* 2 + 2* 1

Responsible for oscillations of the e- intensity at screen

(ii) Stationary state

Probability is independent of time

for every expectation value is constant in time
(ii) Definite total energy
Classical mechanics : total energy is Hamiltonian

Quantum mechanics : corresponding Hamiltonian operator

thus equation (2.2)

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 Applications of
Quantum Mechanics

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1. Particle in a box/ infinitely potential well
2. Finite potential well
3. Potential barrier(tunnel effect)
4. Simple Harmonic Oscillator

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 Particle in a box with “Infinite Hard walls”
+ x0 Boundary conditions and normalization determines 

U(x) = 0 0xL

+ x L

Since the walls are impenetrable, there is

zero probability of finding the particle
outside the box.
Zero probability means:
ψ(x) = 0, for x  0 and x  L

The wave function must also be 0 at the

walls (x = 0 and x = L), since the
wavefunction must be continuous

Mathematically, ψ(0) = 0 and ψ(L) = 0 25

 Schrödinger Equation
 2  2 x 
  U ( x) x   E x 
2m  2 x
for Particle in a Box
For 0 < x < L, where U(x) = 0, the Schrödinger
equation can be expressed in the form

 2  2 x
  E x
2m  x 2

We can re-write it as
 2 x  2 mE
   x 
 x
2
 2

 2 x 
  k 2
 x 
 x
2

2 mE
k 
2
2 26
   x 
2
  k  x 
2
 x
2

The most general solution to this differential

equation is:
ψ(x) = A sin kx + B cos kx
A and B are constants which are determined from the
properties of the ψ as well as boundary and
normalization conditions
1. Sin(x) and Cos(x) are finite and single-valued functions

2. Boundary Condition: ψ(0) = ψ(L) = 0

• ψ(0) = A sin(k0) + B cos(k0) = 0  B = 0
 ψ(x) = A sin(kx)
• ψ(L) = A sin(kL) = 0  sin(kL) = 0  kL = nπ, n = ±1, ±2…
27
 
kn  n n  1,2,3...
L
Particle in a Box
2  2
Energy  ( n )
 2 kn
2
L   2 2
   h 2
 2
Levels: En     n  
2 
2
n
2 
2m 2m  2mL   8mL 
• The allowed wave functions are given by
 n 
ψn(x)  A sin x
 L 

• The normalized wave function:

2  n 
ψn(x)  sin x
L  L  28
 2  n  ψ4
2 2
ψn(x)  sin
L  L
x
 ψ4 ψ n(x)
2
ψ3
ψ3
2
ψ2
ψ2
2
ψ1 ψ1

 2 2  2 2
En  n 2  E0 n 2 , with E0 
2mL 2 2mL 2
ground state (n  1) energy , E1  E0

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Ex-1: e- in a 10nm wide Well with infinite barriers. Calculate E0 for L = 10 nm
3.14 2 (1.05 10 34 ) 2
 2 2 E0 
En  E0 n , where E1  E0 
2 2  9.110 31  (10 10 9 ) 2
2mL2 E0  6 10  22 J  0.00375 eV  3.75 meV
1 meV  10-3 eV

Ex-2: Assume that a photon is absorbed, and the

electron is transferred from the ground state (n =
1) to the second excited state (n = 3). What was
the wavelengths of the photon?

Eground  E1  E0  0.00375 eV
Second excited state is E3
E3  E0  32  9  0.00375 eV  0.0338 eV
( h )  E3  E1  0.0338  0.00375  0.030 eV
1240
λ  41333 nm  41μm 30
0.03 30
Average Momentum of Particle in a Box (Infinite Potential Well)
problem
  *
L
 p x    ( x)
*
 ( x)dx
0
i x
2
L  sin kx
2 
 [ sin kx] L dx
0
L i x
L
2
 k  sin( kx) cos( kx)dx  0
L i 0
Note: the right hand side is either 0 or imaginary, but
momentum cannot be imaginary so it must be zero

But

 p  0
2
x
Why ???
31
 Application No. 2 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
32
 Finite Potential Well
Schrödinger Equation
 2  2 x
  U( x) x  E x
2m  x 2

I. x < 0; U(x) = U
 2 d 2 I
 2
 U I  E I
2m dx
II. 0 < x < L; U(x) = 0
 2 d 2 II
 2
 E II
2m dx

III. x > L; U(x) = 0

 2 d 2 III
 2
 U III  E III
2m dx
33
 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 of SE is
♣ Boundary conditions,
ψII(x) = F sin kx + G cos kx however, no longer
require that ψ(x) be zero
:F and G are constants at the sides of the well
34
 Finite Potential Well: Regions I and III
The Schrödinger equation for these regions is
 2 d 2
 2
 U  E
2m dx
It can be re-written as
d 2 2m(U  E ) 2m(U  E )
   C 2
 , where C 2

dx 2 2 2
The general solution of this equation is
ψ(x) = AeCx + Be-Cx
A and B are constants
Note (E-U) is the negative of kinetic energy, -Ek
In region II, C is imaginary and so have
sinusoidal solutions we found
In both regions I and III, ψ(x) is exponential 2mU
C

35
 Finite Potential Well: Regions I and III
Requires that wavefunction, ψ(x) = AeCx + Be-Cx
not diverge as x  ∞

So in region I, B = 0, and ψI(x) = AeCx

to avoid an infinite value for ψ(x) for large negative
values of x

In region III, A = 0, and ψIII(x) = Be-Cx

to avoid an infinite value for ψ(x)

for large positive values of x
36
 Finite Potential Well
• The wavefunction and its derivative must be single-valued
for all x
– There are two points at which wavefunction is given by two
different functions: x = 0 and x = L
Thus, we equate the two expressions for the  and its
derivative at x = 0, L
This, together with the  I (0)   II (0)
normalization condition,
d I d II
determines the amplitudes of 0   0 
the wavefunction and the dx dx
constants in the exponential  II ( L)   III ( L)
d II d III
term. L  L
This determines the allowed dx dx
energies of the particle
37
 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
zero

 h2  2
En   n
2 
 8mL 

38
 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 of finding the
particle decreases
exponentially, but it is not
zero!

http://phys.educ.ksu.edu/vqm/html/probillustrator.html
39
 Tunneling
The potential energy has a
constant value U in the region
of width L and zero in all other
regions
This a called a barrier

U is the called the barrier

height. Classically, the particle
is reflected by the barrier

Regions II and III would be forbidden

• According to quantum mechanics, all regions are accessible

to the particle
– The probability of the particle being in a classically forbidden region
is low, but not zero
– Amplitude of the wave is reduced in the barrier
– A fraction of the beam penetrates the barrier
40
 Simple Harmonic Oscillator(SHO)
Harmonic Motion:
Vibrates about an equilibrium configuration

Condition: presence of restoring force that acts to return

the system to its equilibrium position when it is disturbed

For SHM:
Classical treatment :

solution
Potential energy V is related to F :

41
 Simple Harmonic Oscillator(SHO)
Quantum treatment :

WHY TO STUDY: Planck postulated that the energy

This approach indentifies several problems: of a SHO is quantized.(In his
1. diatomic molecule model vibrating charges act as
2. an atom in a crystal lattice etc simple harmonic oscillators
3. explain blackbody radiation; and emit EM radiation)

Let’s write down the Schrödinger Equation

for SHO
For SHO the potential energy is
kx2 m 2 x 2
U ( x)  
2 2
k

m
 Simple Harmonic Oscillator(SHO)
Time independent Schrödinger Equation for SHO in 1D
 2  2 x  m 2 x 2
   x   E x 
2m  x 2
2
Solutions: To obtain  and E

1  d 
2

  i   mx    E
2
........................(1)

2m  dx  


Algebraic Method

43
rewrite equation (1) by ladder operator :

compare equation(1)

similarly

44
Discussions

45
 Simple Harmonic Oscillator(SHO)
There must exist a min state with so the ladder of stationary
states can illustrate :
 1
En   n   n = 0, 1, 2,….
 2
m 2

 n x   An a  e
n x
2

and from

46
 Energy of SHO from the Schrödinger equation

1 Term ½hν tells us that quantum SHO always

E  nh  h oscillates. These are called zero point vibrations
2
 The zero point energy ½hν is required by the Heisenberg uncertainty
relationship

 The term of ½hν is important for understanding of some physical

phenomena

 For example, this qualitative explains why helium does not

become solid under normal conditions:
the “zero point vibration” energy is higher than the “melting energy”
of helium

 Force between two metal plates

47
• Decaying wavefunction
tunnels into classically forbidden
region
• Spatial average for high energy
wavefunction gives classical
result: another example of the
CORRESPONDENCE PRINCIPLE
48