Dr.

Pradeep Samantaroy
Department of Chemistry
Rayagada Autonomous College, Rayagada
[email protected]; [email protected]
9444078968
Understanding the Case
Quantum Approach

O < x ≤ Lx
O < y ≤ Ly
O < z ≤ Lz

V (x,y,z) = 0 V (x,y,z) = ∞

Prepared by Dr. Pradeep Samantaroy

 Let’s solve the case…!

The Schrodinger’s equation for the electron in three dimensional

box can be represented as

 2 2
  (r )  V (r ) (r )  E (r )
2m

It can also be represented as

  2  d 2 (r ) d 2 (r ) d 2 (r ) 
 2  2
 2 
 V (r ) (r )  E (r )
2m  dx dy dz 

Prepared by Dr. Pradeep Samantaroy

 Outside and on the Edges of Box

Applying boundary conditions outside the box

Boundary conditions
ψ(0,y,z) = ψ(Lx,y,z) = 0
Ψ(x,0,z) = Ψ(x,Ly,z) = 0
ψ(x,y,0) = ψ(x,y,Lz) = 0

 2 2
  (r )   *  E  0
2

2m

Hence, the probability of finding electron outside the 3D box is zero.

Prepared by Dr. Pradeep Samantaroy

 Inside the box

  2  d 2 (r ) d 2 (r ) d 2 (r ) 
 2  2
 2 
 E (r ) Since V (r )  0
2m  dx dy dz 

To solve this equation, separation of variable can be applied.

ψ(x,y,z)= X(x) Y(y) Z(z)

Now we can see that each function has its own variable:
X(x) is a function for variable x only
Y(y) is a function of variable y only
Z(z) is a function of variable z only
Prepared by Dr. Pradeep Samantaroy
Now substituting the value of Ψ (x,y,z) in the Schrodinger’s equation and then
dividing the whole by xyz,

Now the final equation can be represented as

  2  1 d 2 X ( x) 1 d 2Y ( y ) 1 d 2 Z ( z ) 
 2
 2
 2 
E
2m  X ( x) dx Y ( y) dy Z ( z ) dz 

Prepared by Dr. Pradeep Samantaroy

We also partition the total energy into its rightful components:

E = Ex​ + Ey​ + Ez​

Now each component can be separated as

  2 d 2 X ( x)
 E x X ( x)
2m dx 2

Does this equation looks similar to what we have studied already!!!

It is the case of particle in 1D box. Hence the solution of x component is

2 n xx
x  sin
Lx Lx
Prepared by Dr. Pradeep Samantaroy
Similarly the y and z component can be represented as

  2 d 2Y ( y ) 2 n y y
 E yY ( y) y  sin
2m dy 2 Ly Ly

  2 d 2 Z ( z) n z z
 E z Z ( z) 2
2m dz 2 z  sin
Lz Lz

Prepared by Dr. Pradeep Samantaroy

Therefore the final solution for a particle in 3D box can be represented as

 2 n x x  2 n y y  2
 n z 
 (r )   sin 
 L sin  L sin z 

L L L 
y  L z 
 x x  y z

8  n xx  n y y  n z z 
 (r )   sin  sin  sin
 
or  
Lx L y Lz  L x  L y  Lz 

8  n xx  n y y  n z z 

or  (r )   sin  sin  sin 
V Lx  L y  Lz 
Prepared by Dr. Pradeep Samantaroy
 Energy
Now the energy of the x component can be written as
2 2
nx h
Ex  2
8mLx
Similarly the energy of the y and z component can be written.
Now the total energy can be written as
2
nx h
2 2
ny h2 2
nz h 2
E  Ex  E y  Ez  2
 2
 2
8mLx 8mL y 8mLz

h  nx2 2
n
2 2 
nz 
E  2  2
y

8m  L x 2
Ly L z 
Prepared by Dr. Pradeep Samantaroy
 If the 3D box is a cube?

If the 3D box is a cube then Lx = Ly = Lz = L

8  n xx  n y y  n z z 

 (r )  sin sin sin
V  L  L  L 


h  xn2 2
n
2 2 
nz 
E  2  2
y

8m  L 2
L L 

E
h2
2
n 2
x  n 2
y n 2
z 
8mL
Prepared by Dr. Pradeep Samantaroy
 Degeneracy in a 3D cubical box

Can any one or all of nx, ny, nz values be zero??

Ground state energy can be calculated using

nx= 1, ny= 1, nz= 1

h2
 
2
3h
E111  2
12
 12
 12

8mL 8mL2
Zero Point Energy

Prepared by Dr. Pradeep Samantaroy

 Degeneracy in a 3D cubical box

For the first excitation state energy can be calculated using following
combination of quantum numbers

(nx,ny, nz) = (2,1,1) or (1,2,1) or (1,1,2)

6h 2
E 211  E121  E112 
8mL2

Corresponding to these combinations of (nx, ny, nz), three different wave

functions and three different states are possible. Hence, the first excited state
is said to be three-fold or triply degenerate.

Prepared by Dr. Pradeep Samantaroy

 Degeneracy in a 3D cubical box-Summary

nx , ny , nz nx2 + ny2 +nz2 Energy Degeneracy

(111) 3 3h2/8mL2 1

(211), (121), (112) 6 6h2/8mL2 3

(221), (212), (122) 9 9h2/8mL2 3

(311), (131), (113) 11 11h2/8mL2 3

222 12 12h2/8mL2 1

(123), (132), (213), (231),

14 14h2/8mL2 6
(312), (321)

Prepared by Dr. Pradeep Samantaroy

 (1,2,3) (1,3,2) (2,1,3) (2,3,1) (3,1,2) (3,2,1)
14
Energy in units of h2/8mL2

(2,2,2)
12
(3,1,1) (1,3,1) (1,1,3)
11
(2,2,1) (2,1,2) (1,2,2)
9

(2,1,1) (1,2,1) (1,1,2)

6

(1,1,1)
3

Prepared by Dr. Pradeep Samantaroy