The Dynamics of

microscopic systems
Description of a quantum mechanical system
 A QM particle cannot have a precise trajectory,
there is only a probability.

 A particle is spread through space like a wave…

There are regions where the particle is more
likely to be found than others.

 To describe this
distribution the
concept of
wavefunction ψ is
introduced, in place
of trajectory.
Description of a quantum mechanical system

A Wave function is a mathematical function that

contains all the dynamical information about the state
of a system.

It determines the particle’s probability distribution;

a kind of blurred version of trajectory.

The concept of the wave function and the equation

governing its change with time were discovered in
1926 by the Austrian physicist Erwin Schrodinger.
 The Schrödinger Equation
For a one-particle, one-dimensional system

time-dependent Schrodinger equation / The Schrodinger wave equation

When the potential energy V is not a function of time but depends

only on x, then

time-independent
Schrodinger equation

Operator Form: Hˆ   E 2 d2

Where, the Hamiltonian operator Hˆ   V ( x)
2m dx2
 The Schrödinger Equation: Justification
For special case with V = 0, SE becomes
d 2 2mE Let, k 2  2mE /  2
  0
dx 2  2

A solution is:   sin( k x) wave with

  2 / k
2 2 2
p k 
E  EK  
2m 2m
h
p  k 

Standard harmonic wave
Experimentally verified
 Solutions of the Schrödinger Equation
• Infinite number of solutions are possible.
• But, solutions which obey the boundary conditions
of the system are only allowed.

Each solution
corresponds to a
particular
wavelength, and
thus a particular E.

Only certain values of Energy are acceptable, i.e. Energy

is quantized.
 (Born) Interpretation of wavefunction
The Wave function Ψ contains all the dynamical information
about the particle it describes.
Ψ: No physical interpretation (can be complex).

Ψ2 (or |Ψ|2 if Ψ complex) is real and related to probability

of finding a particle.
 (Born) Interpretation of wavefunction
Probability of finding a particle in a small region of space
of volume dx is proportional to |ψ|2 dx

Curvature d2ψ/dx2
relates to kinetic energy

 ψ2 is probability density  2 d 2
 V ( x)  E
 ψ is probability amplitude 2m dx2
 Acceptable wavefunction

Must be:
a) single valued

b) finite

c) Continuous

d) continuous
slope
 The uncertainty principle
ψ = sin(2πx/λ)
corresponds to p
= h/λ but with no
precise position!

An infinite no. of waves (momenta) are needed to

create the ψ of a well-defined particle.
 The (Heisenberg) uncertainty principle
It is impossible to specify simultaneously, with
arbitrary precision, both the momentum and the
position of a particle.
Position-momentum
p x x   / 2 uncertainty relation
x, px : uncertainty in position and momentum

Sphere: x, Arrow: p
(a) ∆p small, ∆x uncertain
(b) ∆x small, ∆p uncertain
 Implications of uncertainty principle

• Position and momenta are complementary

(i.e not simultaneously specifiable !)

• We can specify position at the expense of

momentum, or vice-versa

• The concept of “Orbit” (a precise position

& momentum of electron) is ruled out.
Applications of quantum
mechanics

1. Translation
2. vibration
 Translation: Particle in a box
Consider a particle with constant potential energy
confined in a one-dimensional region (Box of length L)

Potential
Inside box:
V = const. = 0
Wall: V = ∞

Due to impenetrable walls, Ψ(x) = 0 at x < 0 and x > L

For continuity of Ψ:
Ψ(x) = 0 at x = 0 and x = L (Boundary conditions)
 Solution of the Schrödinger Equation
2
d 
SE for V = 0:  k 2 0 where, k 2  2mE /  2
dx2
  sin( k x)
wave with
A solution is:   2 / k
Ψ needs to satisfy the boundary conditions,
Ψ(x) = 0 at x = 0 and x = L
i.e. each acceptable Ψ must fit inside the box exactly

λ = 2L λ=L λ = 2L/3

0 L 0 L 0 L

In general,   2L / n, n  1, 2, 3
 The Schrödinger Equation: Solution
d 2
With V = 0  k 2  0 where, k 2  2mE /  2
dx2
A solution is   sin( k x) wave with   2 / k
With the boundary condition,   2L / n, n  1, 2, 3
k  2 /    n / L
2
k  ( n / L) (h / 2 )
2 2
nh 2 2 2
En   
2m 2m 8mL2
 n ( x)  N sin( n x / L), n  1, 2
N: Normalization constant
Normalization constant (N) is chosen such that
the total probability of finding the particle is one

1   |  |2 dx Normalization

L
 
) dx  N    N   2 
1/ 2
n x
1  N  sin (
2 2 2 L
0
L 2 L

 (ax)dx
2
sin
n x
1/ 2
2
x sin( 2ax)  n ( x)    sin( )
   L L
2 4a
 const n  1, 2
 Permitted Energy levels & wavefunctions
 n  (2 / L) sin( n x / L) En  n 2 h 2 /(8mL2 )  n E1
2
n  1,2,3,

Zero-point energy
 Lowest irremovable
energy
h2
E1 
8mL2
 Existence is in
consistent with
uncertainty
principle

No. of Nodes: n - 1
 Energy difference between adjacent levels
2
h
E  En1  En  (2n  1) 2
8mL
Smaller Size

Larger Size
∆E

∆E

Greater the size/mass of the system, less important

are the effects of quantization
 PID SUMMARY…
2
d 
 k 2  0 k 2  2mE /  2
PE= 0 dx2
Eigen values & eigenfunctions:
n2h2 2
1/ 2
n x
En   n ( x)    sin( )
8mL2 L L
h2 Zero-point energy
E  En1  En  (2n  1)
8mL2 E1

 n dx  1
 2
Normalized function: | |

  dx  0
*
Orthogonal functions: n n'

Orthogonal + Normalized ≡ Orthonormal

 Particle-in-a-box with finite barrier

Let E < V0
(i.e. classically the particle can
not escape the container)

Although E < V0, the probability of finding particle outside the container
is NOT zero. Such leakage by penetration into or through classically
forbidden region is called tunnelling.

Transmission probability:
2 a Particles of low mass are more able to tunnel
T  16 (1   )e through barrier than heavy ones:
  2m(V0  E ) /  more important for electrons, moderate important
for protons, and negligible for most other heavier
  E / V0 particles.
 Application of Tunnelling

A scanning tunnelling
An STM image of
microscope makes use of
the current of electrons that caesium atoms on a
tunnel between the surface gallium arsenide
and the tip. surface
 Translation: Motion in two dimensions
A particle with constant potential energy in a two-
dimensional region with impenetrable walls at both
sides
Potential
Inside 2D box:
V = const. = 0
Wall: V = ∞

Separation of variables technique, which divides

the equation into two ordinary differential equations,
one for each variable.
Translation: Motion in two dimensions
Wavefunctions…
 Degeneracy

(square plane surface):

Consider the cases:

n1  1, n2  2
and
n1  2, n2  1

 Although the wavefunctions are different, they correspond to

the same energy (degenerate).
 The occurrence of degeneracy is related to the symmetry of
the system.
 Vibration: The harmonic oscillator

Harmonic vibration follows Hooke’s Law of force

Restoring force, F = -k x
k: is the force constant,
x: is the displacement

dV
F  
dx
kx 2
V 
2

Parabolic potential: characteristic of a harmonic Oscillator

Positive displacement: extension
 The harmonic oscillator: Solution
Potential energy varies with coordinate. SE becomes
2 2
 d  1 2
  kx   E
2m dx2 2

Energy Levels:
1
E  (  )h
2
  0,1, 2
1 k

2 m
E  E 1  E  h
 The harmonic oscillator: Solution
Wavefunctions are given as Hermite polynomials

No. of nodes: V
 The probability
distributions

Tunnelling →