GENERAL CHEMISTRY (CHEM F111)

Lecture 6: 02/11/2022

Recap
 Particle in a one dimensional
box
 Energy eigenvalues and
eigenfunctions
 Zero-point energy
 Probability
Normalized wavefunction/eigenfunction

n=1,2,3….

n can not be zero; then =0

everywhere and particle vanishes;
2 2
nh
Allowed Eigenvalues En  2
8mL
Energy levels are quantized
 Wavefunctions of Particle in a 1D box

2  nx 
 ( x)  sin  
L  L 

n 2h 2  *
E 2 n = 1, 2, …
8mL
Energy is quantized
 Tunneling
•Crossing of potential barrier by a
quantum particle

•Has no classical analogy

•A purely quantum phenomena
•The wavefunction of the particle is non-
zero beyond the wall
•Particle has a probability to be observed
beyond the wall – can tunnel through
Tunneling
V
Classically forbidden
region
ψ 0 ψ 0
 Tunneling
•Crossing of potential barrier by a quantum
particle

Classical Tunneling occurs only in Harry Potter movies!

•If the potential barrier is not infinitely high,
then the wave function may not go to zero at
wall and
• can pass/penetrate through the barrier
•The wavefunction of the particle is non-
zero beyond the wall
•Particle has a probability to be observed
beyond the wall – can tunnel through

Tunneling happens
• When the walls are thin
• Particle is very light
 Particle in a
rectangular well

•Implies the wave nature of the particle

 Tunneling probability decreases rapidly with increasing
barrier width/height, and increasing particle mass.
Important for electron transfer, proton transfer, etc.,
Applications of Tunneling

1. Electrochemistry : in electron and proton

transfer reactions

2. Biology

3. Semi- conductor industry

4. Scanning Tunneling Microscopy

5. Atomic Force Microscopy

 Applications of Tunneling
1. Scanning Tunneling Microscope (STM)
STM) is a powerful instrument for imaging
surfaces at the atomic level
 Applications of Tunneling
1. Scanning Tunneling Microscope (STM)
STM) is a powerful instrument for imaging
surfaces at the atomic level

Image of reconstruction on a STM image of Fe positioned

clean Gold surface. on Cu Surface
Delightful explanation
of the central concepts
in modern physics, from
atomic structure to
relativity, and quantum
theory to fusion and
fission.
 Particle confined in a two-dimensional
box or confined on a surface

y
V= 

V=  V=0 V= 

x
0 V=  a
Particle in a 2-D Box Hamiltonia n and
Schrödinger eq. in 2D
Total Energy of particle E = E kin  E pot

1
E [ p x2  p y2 ]  V ( x, y )
2m
Transition to QM
 d  d
pˆ  ; pˆ 
x i dx y i dy
 2 2 2
H  [  ]  V ( x, y )
2m x 2 y 2

Employ method of separation of variables to get two

independent ordinary differential equations
Schrödinger Equation

Ĥψ = Eψ

Particle in a 1 - D Box
 2 d 2
 2
 V ( x)  E
2m dx

Particle in a 2 - D Box
 2  2 ( x, y )  2 ( x, y )
 [  ]  V ( x, y ) ( x, y )  E ( x, y )
2m x 2
y 2
Particle in a 2-D Box

Method of Separation of Variables

1/ 2
 4   n X x   nY y 
 nx ,n y ( x, y )    sin   sin  
 LX LY   LX   LY 
2 2 2 2
nx h n yh
En x , n y  
2
8mLX 8mL2Y

Wave function is a product of two individual one

dimensional wave functions.
Total energy is a sum of two energy eigenvalues
 Particle in a 2-D Box
For a Square Box
When L x  L y  L
 2   nxx   n yy 
 nx ,n y ( x, y )    sin   sin  
L  L   L 
2
h
En x , n y  (nx2  n y2 )
8mL2

Wave function is a product of two individual one

dimensional wave functions.
Total energy is a sum of two energy eigenvalues
Degenerate States
For n x  1 and n y  2
2  x   2y 
 1, 2 ( x, y)  sin   sin  
L L  L 
2 2
h 5h
Enx ,n y  (n  n )
2
x
2
y 
2
8mL 8mL2
For n x  2 and n y  1 E1,2 = E2,1
2  2x   y  Degeneracy happens
 2,1 ( x, y)  sin   sin  
L  L   L  Only because of symmetry

2 different states,
but have the same energy ; degenerate states
Degenerate States 2
h
En x , n y  (nx2  n y2 ) 2
8mL

nx ny k (h2/8mL2)
k
1 1 2 Non/singly-Degenerate
1 2 5
Doubly Degenerate
2 1 5
2 2 8 Non/singly-Degenerate
2 3 13
Doubly Degenerate
3 2 13
 n
Thought Question : n2
For ψ2, the maximum probability to find the
Particle is at L/4 and also at 3L/4. i.e. You can
locate the particle in both halves of the box.

But you cannot locate the particle in between,

in the middle of the box at L/2. Why?
Probability Density Distribution
 Orthogonality
  If m=n
     
* *
dx 1 dx 1 Normalization
m n n n
 

mn
  
* If
m n dx 0

wavefunctions are orthogonal to each other.
they must have different eigenvalues to obey
orthogonality condition. Not obeyed for degenerate
states!
 Vibration: Harmonic Oscillator

-x +x

Vibrational spectra of diatomic molecules

Complex modes of vibrations of large
molecules
Motion of atoms in solid lattice
Theory of heat capacity
 Vibration: Harmonic Oscillator

Hooke’s law: Restoring force =  kx ( k – force constant,

x – displacement from equilibrium)
Potential energy V(x) = ½ kx2
 Vibration: Harmonic Oscillator
Hooke’s law: Restoring force F =  kx
Force is gradient {x +y +z  } of potential
energy; derivative (x ) in one dimension (x):
F = - dVdx
dV = - Fdx

Total P.E is dV over whole range of x

x x
V(x) – V(0) = -  Fdx    kxdx
0 0

Potential energy V(x) = ½ kx2

A parabolic equation
 Schrödinger equation
 2 d 2
 2
 V ( x)  E
2m dx
1 2
V  kx
2
 2 d 2 ( x) 1 2
 2
 kx  ( x)  E ( x)
2m dx 2
Eυ = (υ + ½)h, υ = 0,1,2,…. is the vibrational
quantum number
1 k
  ; neu
2 m
Eυ = (υ + ½)h

Equally spaced
energy levels.
Spacing = h
Ground state
energy = ½ h
(Zero point energy)
 Evenly spaced energy levels.
Spacing = h
Ground state energy = ½ h
(Zero point energy)

Energy of a system described by a harmonic

oscillator potential cannot have zero energy. Atoms in
a solid lattice or in polyatomic molecules in a gas
cannot have zero energy even at absolute zero
temperature. "zero point vibration".
 Energy Levels
- +

Solve the Schrodinger equation and apply the

boundary conditions (   as x  ) to get:
Eυ = (υ + ½)h,
υ = 0,1,2,…. is the vibrational quantum number,

1 k

is the vibrational frequency. 2 m
Harmonic Oscillator wave functions
Harmonic oscillator Wavefunctions

1. Number of nodes is υ.
2. Wavefunctions alternately symmetric
or antisymmetric about x = 0.
 Characteristics
3. One can show that as υ becomes large, the
probability distribution resembles the classical
result.
 Characteristics
4. The wavefunction penetrates into the classically
forbidden region –TUNNELING.

Vibrational (infrared) spectroscopy

The probability distributions

correspondence principle –
the results are more classical as
v increases