General Chemistry (CHEM

F111)

Lecture-5
23/01/2024
Recap
1. Schrodinger eqn. (Eqn. for de Broglie
wave)
2. Well-behaved wavefunction for a
physical system
3. Operators, and Eigen value equation
4. Solutions to Schrodinger equations for
(i) a free particle
(ii) a particle in 1D box
Today’s topic

1.Wavefunctions and Energy of particle in

1D Box
2. Spectroscopy using particle in 1D Box as
the model
3. Solutions to Schrodinger equations for
a particle in 2D box
 Particle in 1D Box

En = n2h2/8mL2 - Quantized energy levels!

n = N sin(nx/L) -Wavefunctions corresponding to the energy levels.
Particles are looked to be as waves :Quantum
view

The ‘particle’ is no more pictured as a particle bouncing

between the walls but a de Broglie wave that is trapped inside
the infinite quantum well, in which they form standing waves
 Wavefunctions

E  
 Characteristics of the wavefunctions - Particle in 1D Box
1. Wavelength = 2L/n
2. There are n-1 nodes (interior points where the
wavefunction passes through zero) in the wavefunction
n. The energy increases with increasing number of
nodes. The ground state has no node.
3. The ground state energy is not 0, but h2/8mL2, the zero
point energy. This is a consequence of the uncertainty
principle. Particle is within the box, so uncertainty in
position, x can not be infinite; px can not be zero.
4. Note the dependence of the energy on L, the size of the
system and m, the mass of the particle. Greater the value
of L or m, the less important are the effects of
quantization. Mass of the particle increases – classical
limit. Size of the box increases – classical limit

En+1 – En = (2n+1)h2/8mL2
Quantization important for highly confined regions, and for
particles of very small mass.
5. Note the symmetry of the wavefunctions – they are all
either symmetric or antisymmetric under reflection about
the middle of the box.
6. As n becomes very large, the probability distribution for the
particle becomes uniform over the entire length of the box.

Classical behavior – correspondence principle

The probability density ψ2(x) for large quantum number (here n = 50, blue, compared with n = 1, red).
Notice that for high n the probability density is nearly uniform, provided the fine detail of the
increasingly rapid oscillations are ignored.
 Particle in a 1D box: Example

 Electrons of a long conjugate polyene, trapped

electrons in a cavity

R
R
L
 Particle in a 1D box: Example

10 single and 11 double bonds alternate along a chain of 22 carbon atoms.

Say, average C-C bond length = 140 pm. So length of molecular box =
140 pm × 21 = 2.94 nm

22  electrons. So in the lowest energy state, each level upto n = 11 is

occupied by two electrons.
E = E12 – E11 =
(122 – 112)[(6.626×10-34 js)2/8×(9.11x10-31kg)(2.94×10-9m)2]= 1.6×10-19 J
= h. So,  = 2.42 × 1014 s-1
Particle in Two Dimensional Box

• V(x,y) = 0 for 0 ≤ x ≤ a, 0 ≤ y ≤ b, ∞ otherwise

• -(ħ2/2m) (∂2/∂x2 + ∂2/∂y2) ψ(x,y) = E ψ(x,y)

• Ĥ(x,y) = Ĥ(x) + Ĥ(y)
• Can use separation of variables method to solve the
equation

• Can show that ψ(x,y) = ψnx(x) ψny(y)

• ψnx,ny(x,y) = (4/ab)1/2 sin(nxπx/a) sin(nyπy/b)

• Enx,ny = (nx2/a2 + ny2/b2)h2/8m

 Particle in Two Dimensional Square
Box
When b = a, Enx,ny = (nx2 + ny2)h2/8ma2

ψnx,ny(x,y) = (2/a)1/2sin(nxπx/a)(2/a)1/2sin(nyπy/a)

= (2/a)sin(nxπx/a)sin(nyπy/a)

The ground state is of energy 2h2/8ma2

Wavefunctions in Two Dimensional Square
Box
nx = 1, ny = 1

nx = 2, ny = 1

nx = 2, ny = 2
Probability Density Distribution