Particle in a Ring: Quantization of Energy

Introduction:
Solving the problem of a particle (of mass m) in a ring (of radius R) is easy if you
have already done particle in a 1-dimensional box. The ring may be viewed as a box
in which the x-axis is bent into a ring of radius R. So, we need to start with the
equation like that of a particle in a box, and incorporate angular position. That means,
we have to replace the wave function (x) by the wave function (). Finally we
have to put the cyclic boundary condition to arrive at quantization.
Let’s start:
Let us start with the SchrÖdinger equation of particle in a box
ℎ2 𝜕 2 (x)
− 8𝜋2 𝑚 = E(x) ...
(1) [h is the Planck’s constant]
𝜕x2
The angular position  of the particle on the ring can be given as:
x
=
𝑅
Eqn. (1) can now be rewritten as
ℎ2 𝜕 2 ()
− 8𝜋2 𝑚𝑅2 2 = E() ...
(2)
𝜕
Recall the solution of particle in a box. We can similarly rearrange Eqn. (2) as
𝜕 2 () 8𝜋2 𝑚𝑅2 𝐸
+ ()= E() ...
(3)
𝜕2 ℎ2
2
8𝜋2 𝑚𝑅2 𝐸 ...
Putting k = (3a)
ℎ2
Eqn. (3) becomes . . .
𝜕 2 ()
2 + k2 () = E() ...
(4)
𝜕
General solution of Eqn. (4) is:
() = Ne±ik ...
(5) [N is the normalization constant]
Now we can use the cyclic boundary condition, which is:
( + 2π) = () ...
(6)
which means
eik(+2π) = eik ...
(7)

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Hence
e2πik = 1; or (−1)2k = 1 ...
(8)
Eqn. (8) will be true only if k is an integer, and has values:

k = 0; ±1; ±2; ±3 . . .
Finally, rearranging Eqn. (3a), we get the value of quantized energy levels Ek:
k2 ℎ 2
𝐸𝑘 = ...
(9)
8𝜋2 𝑚𝑅2

Cyclic Conjugated Hydrocarbon (CnHn) & Energy of -molecular orbitals:

This is a special case of particle in a ring and Huckel theory gives a full picture of the
energy of the -molecular orbitals.
Please only note that in this case:
n
k = 0; ±1; ±2; ±3 . . . . . . (for even n)
2
(n−1)
k = 0; ±1; ±2; ±3 . . . ± . . . (for odd n)
2
Aromatic Molecules – an example:
The benzene molecule [C6H6, so n=6] consists of a ring of 6-carbon atoms around
which 6- delocalized -electrons can circulate. So, the MO picture will be [red dots
are electrons]

The HOMO to LUMO transition wavelength can be easily calculated with the help of
Eqn. 9. Use m as the mass of an electron, h as Planck’s constant, C-C bond length as
139 pm. So radius will also be 139 nm. The calculated wavelength comes to 210 nm.
Experimental value is 268 nm.
Happy reading.
Sujit Roy
sroy@iitbbs.ac.in
9439365740

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