2- Particle in a 2-D Rectangular Box

Schrodinger Equation is

( ) ( ) ( ) ( )

Inside the box V=0 then

( ) ( ) ( )

This equation has the following solution

( ) ( ) ( )

( )
 𝑛 𝑛
𝐸𝑛 𝑛 ( )
𝑚 𝐿 𝐿

1 1
𝐸 ( )
𝑚 𝐿 𝐿

4 1
𝐸 ( )
𝑚 𝐿 𝐿

4 4
𝐸 ( )
𝑚 𝐿 𝐿
Degeneracy
Two (or more) different states with the same energy = Degenerate

𝑛 𝑛 𝑛 𝑛
𝐸𝑛 𝑛 ( ) 𝐸𝑛 𝑛 ( )
𝑚 𝐿⬚ 𝑚 𝐿 𝐿

Degenerate states –same energy

Different wave functions related by symmetry
Degeneracy = 2

Nodal Planes:
( )
 Examples:
 Draw the following wave functions and give their energies

 As a variant on the free-electron model applied to benzene,

assume that the six  electrons are delocalized within a square
plate of side L=4.2 Å. Calculate the 1st π→ π* transition and
compare it to experimental value 200 nm.

 Azulene C10H8, shown below, is an aromatic hydrocarbon

containing delocalized π electrons. As a model for this π -
electron system, consider the mobile electrons in a rectangular
two-dimensional box of dimensions 5.00 Å by 4.65 Å.
1- How many π -electrons does azulene have?
2- Identify the quantum numbers of the HOMO and LUMO of
the π electron system
3- Calculate the wavelength (in nm) of the lowest-energy π
electron transition
4- Should azulene be a colored compound?
 Naphthalene C10H8, shown below, is an aromatic hydrocarbon
containing delocalized π electrons. As a model for this π -
electron system, consider the mobile electrons in a rectangular
two-dimensional box of dimensions 5.60 Å by 4.40 Å.
1- How many π -electrons does naphthalene have?
2- Identify the quantum numbers of the HOMO and LUMO of
the π electron system
3- Calculate the wavelength (in nm) of the lowest-energy π
electron transition
4- Should naphthalene be a colored compound?
 3-Particle in a 3-D Box

Schrodinger Equation is

( ) ( ) ( )

( ) ( )

Inside the box V=0 then

( ) ( ) ( ) ( )

This equation has the following solution

( ) ( ) ( ) ( )

( )
Degeneracy of Particle in a 3-D Box
 Two (or more) different states with the same energy = Degenerate

( )

 In the Cubic box

( )

 The lowest level E111 is non-degenerate but the second level is

threefold degenerate

 The degeneracy occurs in the symmetric cube while in the general

rectangular box the degeneracy is destroyed because the symmetry
is destroyed by making the sides with different lengths.
 Examples:
 Assume that a nucleus can be represented as a cubic box of side
10-14 m. The particles in this box are the nucleons (protons and
neutrons). Calculate the lowest allowed energy of a nucleon.
Express your result in MeV (1 MeV = 106eV, Mn = 1.67 x 10-27
kg).

 Consider the hypothetical reaction of two "cube-atoms" to form a

"moly-box". Each cube-atom contains one electron. The
interaction between electrons can be neglected. Determine the
energy change in the reaction. Comment in your results.