Ch41.

   Atomic  Structure  
41.1  –  Schrodinger’s  Equa:on  in  3  –D  
41.2  –  Par:cular  in  a  “3-­‐D  box”  with  infinite  
poten:al  wall  

Ph274  –  Modern  Physics  

3/16/2016  
Prof.  Pui  Lam  
 Learning  Outcomes  
(1) Understand  how  to  extend  the  1-­‐D  
Schrodinger’s  equa:on  to  3-­‐D  
(2) Understand  the  energy-­‐eigenstate  solu:ons  
to  the  “par:cle  in  a  3-­‐D  box”  model.    
Compare  the  solu:ons  to  those  for    1-­‐D.  
(3) Understand  the  meaning  of  “degeneracy”.  
 Compare  1-­‐D  and  3-­‐D  Schrodinger  Equa:on  
! 2 ∂ 2 Ψ(x,t) ∂Ψ(x,t)
1− D : − + U(x)Ψ(x,t) = i!
2m ∂x 2
∂t
For state with definite energy → Ψ(x,t) = ψ (x)e−iEt /!
! 2 d 2ψ (x)
⇒− 2
+ U(x)ψ (x) = Eψ (x)
2m dx
(K.E.) + (P.E.) = Total Energy
! 2 ∂ 2 Ψ(x, y, z,t) ! 2 ∂ 2 Ψ(x, y, z,t) ! 2 ∂ 2 Ψ(x, y, z,t)
3− D :− − −
2m ∂x 2
2m ∂y 2
2m ∂z 2
∂Ψ(x, y, z,t)
+U(x, y, z)Ψ(x, y, z,t) = i!
∂t
For state with definite energy → Ψ(x, y, z,t) = ψ (x, y, z)e−iEt /!
! 2 ∂ 2ψ (x, y, z) ! 2 ∂ 2ψ (x, y, z) ! 2 ∂ 2ψ (x, y, z)
⇒− − −
2m ∂x 2
2m ∂y 2
2m ∂z 2
+U(x, y, z)ψ (x, y, z) = Eψ (x, y, z)
Review particle in a 1-D box:
ψ (x,t) = ψ (x)e−iEt /! = [A cos(kx) + Bsin(k)]e−iEt /! for 0 ≤ x ≤ L
ψ (x = 0) = 0 = ψ (x = L) ⇒ Choose only the sine function
and only certain k's are allowed:
nπ x −i E!n t
⇒ ψ n (x,t) = An sin( )e
L
! 2 ⎛ nπ ⎞ 2 ! ⎛π⎞
2 2 2

En = ⎜⎝ ⎟⎠ = n ⎜ ⎟ (Energy is quantized)
2m L 2m ⎝ L ⎠

Similar  to  
standing  wave  
For  vibra:ng  
string  with  both  
end  fixed.  
 Par:cle  in  a  3-­‐D  box  
Inside the box, the potential energy = 0.
! 2 ∂ 2ψ (x, y, z) ! 2 ∂ 2ψ (x, y, z) ! 2 ∂ 2ψ (x, y, z)
− − − = Eψ (x, y, z)
2m ∂x 2
2m ∂y 2
2m ∂z 2

for 0 ≤ x ≤ L; 0 ≤ y ≤ L; 0 ≤ z ≤ L
Infinite potential wall ⇒at x = 0, x = L, y = 0, y = L, z = 0, z = L,ψ (x, y, z) = 0
So, what is expression for ψ (x, y, z)?

Work out solution on the board.

 Par:cle  in  3-­‐D  Box  answer  
ψ (x, y, z) = X(x)Y (y)Z(z)
⎛ n πx⎞ ⎛ n πy⎞ ⎛ n πy⎞
3
⎛ 2⎞
= ⎜ ⎟ sin ⎜ X ⎟ sin ⎜ Y ⎟ sin ⎜ Y ⎟ ;
⎝ L⎠ ⎝ L ⎠ ⎝ L ⎠ ⎝ L ⎠
n X = 1,2, 3,...;nY = 1,2, 3,...;nZ = 1,2, 3,...

! 2π 2
EN X ,NY ,N Z = ( n X 2
+ nY + nZ )
2 2

2mL2

3
⎛ 2⎞
The "nomarlization" factor ⎜ ⎟ is to esnure that the total probably=1
⎝ L⎠
L L L

⇒ ∫ ∫ ∫ ψ 2
| (x, y, z) | dxdydz=1
0 0 0
Energy  levels  for  a  par:cle  in  a  3-­‐D  Box  

Degeneracy  =  3