Chapter 5

Spherically Symmetric Potentials

.
In this chapter we are going to solve the radial equation (eq.27) in the previous
chapter) for several particular cases. Recalling the radial equation we have

 2 d 2U  l l  1 2 

    V r U r   EU r  (1)
2 dr 2 
 2r
2 

With U(r) =rR(r) and the condition U(0) =0 for  to be finite at r=0.

The Free Particle V(r) =0

Let us first solve the problem of the 3-dimensional free particle in Cartesian
coordinates. The Schrödinger Eq. becomes

2 2
    E ( 2)
2
Letting r   X  x Y  y Z  z   (3)

 2  d2 d2 d 2 
 YZ 2 X  XZ 2 Y  XY 2 Z  EXYZ (4)

2  dx 
dy dz 
 Deviding Eq.(4) by r   X  x Y  y Z  z  

 1 d2 
   2 E
2 2
 1 d 1 d
X  Y  Z (5)
 X dx 2 Y dy 2 Z dz 2  2

Since each term of the L.H.S of the above equation (Eq.(5)) depend on different
independent variables and their sum equals to some constant then each term
must equal to a constant such that

d2 d2 d2
2
X  x   k 2
x X  x   0, 2
Y  y   k y Y  y   0,
2
2
Z  z   k 2
z Z z   0 ( 6)
dx dy dz
2
with k x2  k x2  k x2  k 2  2
E (7)

The solutions of Eqs.(4) are

X  x   C x e ik x x , Y  y   C y e , and Z  z   C z e ik z z
ik y y


 r   C k  e ik r
(8)
The Free Particle as a Central Force Problem
Solving the free particle in spherical coordinates and letting
r   Y  ,  Rr  (9)

To find R(r) we have to solve the radial Eq. which now becomes

  2 d  2 d  l l  1 2 
 r   Rr   ERr  (10)
 2r 2 dr  dr  2r 
2

2E d dρ d
 
d

Introducing the dimensionl ess variable   r  kr  k
 2 dr dr dρ dρ

d 2 R   2 dR   l l  1 
  1   R    0 (11)
d 2  d   
2

As a special case let us consider Eq.(8) for l=0. The equation becomes

d 2 R   2 dR 
  R    0 (12)
d 2  d
 U  
Letting R   with U 0  0 

dR  U   1 dU   d 2 R   2U    2 dU    1 d 2U   
 2  and   2 
d   d d 2
 3
 d  d 2

Eq.(12) then becomes

1 d 2U   U   d 2U  
 0  U    0 
 d 2  d 2

U     A sin   B cos  
sin  cos 
R    A B (13)
 
sin 
For R not to diverge B=0, then R    A

The two linearly independent solutions to Eq.(8) for any l are called the
spherical Bessel's functions, i.e.,
 R    Al jl     Bl nl    (14)

Where jl and nl are called, respectively, the lth order spherical Bessel and
spherical Neumann functions.

As it is clear from the graphs we have nl     

 0
The spherical Neumann functions are not acceptable solutions

 2k 2
  r , ,    jl kr Y  ,   with E  (15)
2
Some Properties of Bessel's Functions:

jl  z   J l  1 z 
2z 2

l
 d   sin z  l
jl ( z )   1 z l 
l
   l l d 
nl ( z )    1 z  
 cos z 
 
 zdz   z   zdz   z 

sin z
j0  z   n0  z   
cos z
z z

sin z cos z
j1  z    n1  z   
cos z sin z

z2 z z 2 z

 3 1  3 1 3
3
j2  z    3   sin z  cos z n2  z    3   cos z  sin z
z z z z z z
 
e  z 2 t 1 t 
  J l  z t l
l  
l 2s
  1  z 
s
J l z    
s 0 s! l  s !  2

J l  z    1l J l  z 

a
    a2
 J  P a  J  q a   d  2 J 1 P   pq
2

0    

a
    2 a3
 jl   lP  jl   lq   d   jl 1  lP 2  pq
0  a  a 2




 lj  z 2
dz 
 2l  1
Now comparing Eqs(6 & 10) 
  m l
e ik r
   Clm jl kr Y  ,   (16)
l 0m  l

As a special case if k (p) is along the z-axis, then Lz=0 (m=0) 


ikr cos 
e ikz
e   al jl (kr ) Pl cos   (17)
l 0
2
Multiplying by Pl(cos) and integrate   ll '
2l  1

1  1
ikr cos
e Pl ' cos  d cos     al jl kr   Pl ' cos  Pl cos  d cos  
1 l 0 1

Using the orthogonality relation of the Legender's functions 

1  2 2
ikr cos
e Pl ' cos  d cos     al jl kr   ll '  al jl kr  
1 l 0 2l  1 2l  1
2l  1 1 ikr cos
al jl kr    e Pl ' cos  d cos   (18)
2 1
Substituting Eq.(18) into Eq.(17) gives
 2l  1 1 ikr cos
ikr cos
e ikz
e   e Pl ' cos  d cos  Pl cos   (19)
l 0 2 1

Using the identity

1
1
jl  z   l  Pl s d s 
e izs
(20)
2j 1

The last equation becomes


e ikz
  2l  1 j l jl kr Pl cos   (21)
l 0

This formula is especially used in scattering theory. Using the addition theorem
for spherical harmonics one can generalize Eq.(21) for any arbitrary direction of
k to be
 
e ik r
 
  2l  1 j l jl kr Pl kˆ  rˆ (22)
l 0
The Square Potential Well:
Consider the potential

 Vo
 r a a
V r    (23) 0 r

 0 r a

The radial equation now reads V0

  2 d  2 d  l l  1 2 
 r   Rr   E  V0 Rr  for r  a (24)
 2r 2 dr  dr  2r 
2

  2 d  2 d  l l  1 2 
 r   Rr   ERr  for r  a (25)
 2r dr  dr 
2
2r 
2

Eq.(24) has the same form as Eq.(7) but now E is replaced by E+V0, that is the
solution of Eq.(24) is again Bessel's function

2 E  V0 
R   Al jl kr  , with k  2
r a (26)

For the exterior region (r > a) the solution must vanish as r  ∞. Since E<0 for
bound states  Eq.(17) has also the same solution as Eq.(7) but k now is an
imaginary number. Defining
nl     
 0

R   Bl hl(1) k ' r  r a (27)

with hl(1)  x   jl  x   inl  x 

Are the spherical Hankel functions which decrease exponentially so that the
boundary conditions Rr     0 is satisfied.
The boundary conditions requires that the two solutions of Eq.( 26 & 27) must
match at r = a and so their derivatives which give a complicated equation.
As a special case let us consider only the ground state (l=0). Eq.(24) and (25)
become with U=R/r
  2 d 2U
   E  Vo U r  ra
2  dr 2

 2 d 2U
  EU r  ra
2  dr 2

The solutions of the above 2-equations are

2 E  Vo 
U r   A sin kr  B cos kr , k  2
ra

 2 E
U r   Ce  qr  De qr , q  2
ra

From the condition that U(0)=0, then B=0, and from the condition U=0 as r ,
then D=0.

U r   A sin kr ra U r   Ce  qr ra

From the condition that U(r) and its derivative must be continuous at r=a we
have
 A sin ka  Ce qa
k
kA cos ka  Cqe  qa  tan ka   (28)
q
a
Letting z  ka and z o  2 Vo 


a2 2a 2 2a 2
zo2  z  2 2Vo   2
2
E  Vo   2
E  a 2 2
q
  

The transcendental equation, Eq.(28) becomes

ak z 1
tan z     
aq zo 2  z 2 zo 2 z 2  1

 cot z  zo 2 z 2  1 (29)

Graphing the functions y   cot z and y  zo 2 z 2  1

It is clear from the graph that there is no solution for zo</2, or for

a  2Vo a 2 2  2 2
2 Vo     V0 
 2  2 4 8a 2
The ground state energy occurs somewhere between /2 < z <, or

 2 2  2 2
 E1  Vo 
8a 2
2a 2
The Coulomb Potential:
The coulomb potential is given by V r    ze 2


r r
The radial equation Eq.(1) now reads

 2 d 2U l l  1 2  
   U r   EU r  (30)
2 dr 2  2r 2 r 

with  U  r U r dr  1 (31)
0
Notice that the radial equation can be though of as a consisting of a radial
kinetic energy term and an effective potential with.
l l  1 2 
Veff   (32)
2r 2 r
There is a positive contribution due to the repulsive potential for l > 0, and a
negative contribution due to the Coulomb attractive potential.
At small r, centripetal potential dominates, and large r both terms approach
zero.
Going back to Eq.(30). Introducing the dimensionless variable
 2E
 2
r  kr (33)

d dρ d d d2 2 d2
  k  k
dr dr dρ dρ dr 2 dρ 2
Eq.(30) then reads

d 2U    2 l l  1 k
 1   2 
U    0, 2  (34)
d 2
    E
Applying the series solution to Eq.(34) we will not obtain a two-terms recurrence
relation. In order to simplify the solution we test the limiting cases,  → 0, and
 → ∞. As  → ∞ , Eq.(34) reduces to
d 2U  
 U    0
d 2

The above equation has a solution (meeting the boundary conditions) of

U    e    e   e   (35)
As r→ 0 the repulsive potential dominates and Eq.(34) reduces to
 d 2U   l l  1
 U    0 l0 (36)
d 2
 2

The series solution of Eq.(36) requires that


U     Cn  n (37)
n 0
 
n
Substituting back in Eq.(36)   Cn n   n    1  l l  1  C n  n    0
n 0 n 0

Equating the coefficient of r to zero  C0    1  l l  1  0 

  l or   l  1
Now equating the coefficient of r+n to zero 
C n n   n    1  l l  1  0 

For   l  C n n  l n  l  1  l l  1  0 

The term in the parenthesis can’t be zero except for n=0.  Cn= 0 except for
C o.
For =l+1, we have C n n  l  1n  l   l l  1  0 

Again Cn= 0 except for Co. Then solution of Eq.(36) reduces to

U     A  l 1  B  l l 1 (38)
but U 0  0  B0 
The solution of Eq.(34) that satisfies the boundary conditions can be written as

U r    l 1 e   W    (39)

dU   dW  
 l  1 l e   W     l 1 e   W     l 1 e  
d d
d 2U   dW ( 
 l l  1 l 1 e   W    l  1 l e   W     l  1 l e   )
d 2 d
l  l 1   l 1   dW (  )
 (l  1)  e W ( )   e W ( )   e
d
l  dW (  ) l 1   dW (  ) l 1   d W (  )
2
 l  1 e  e  e
d d d 2
Eq.(34) now becomes

d 2W
 2  2l l  1W  0
dW
  2l  1    (40)
d 2 d

Applying the series solution to Eq.(40) 


W      Cn  n (41)
n 0
Substituting back in Eq.(40) 
   
 Cn nn  1 n 1
 2l  1  C n n n 1
 2  C n n  2  2l  1  C n  n  0
n
n 0 n 0 n 0 n 0

Equating the coefficient of n to zero 

C n 1 nn  1  2l  1n  1  2n  2  2l  1C n 

2n  l  1  2
Cn 1  Cn (42)
n  1n  2l  2
It is clear from Eq.(42) that

Cn 1 2

Cn n  n

Let us now examine the series

2
 2n  n Cn 1 2 n 1 n! 2
e      
n 0 n! Cn n  1! 2 n
n

w   behaves like e 2  for large   The solution given by Eq.(39) which is

U r    l 1 e   W   

diverges at infinity and that violates the boundary condition. To overcome this
dillemma, we have to terminate the series after a finite number of terms say N
 from Eq.(42) we let

C N 1  0   N  l  1   
   N  l 1 Bohr-Atom: Bohr postulated that electrons
circulates around the nucleus such that the
Since l & N  0,1,2,  angular momentum is quantized, i.e., L  n
  1,2,  n  e2 v 2 e2
  r
n  N  l 1  l  n 1 r 2 r v 2
Now as   n
L n
 But L  vr  v   
r r
 2k 2 2
n  
2 2
rn 2
n 2
ao
4E 2 e 2

2 z 2 e 4 From the 1st Eq. we have T   12 V 

n   
2 2

4E  2 2
e
Now E  12 v 2   T  12 V
r
z 2 e 4 z 2e 2
E  e 2
2n 2
2ao n 2 E   12 v   12
2

r
2
2 E 2
e
with ao  is the Bohr radius
e 2 2n ao
Now rewriting Eq.(40) as

 d 2W dW
 l  1     NW  0 (43)
2 d 2 d

Letting z  2  , p  2l  1, q  N  2l  1  n  l 

d 2W dW
z 2   p 1 z  q  p W  0 (44)
dz dz
Eq.(44) is the associated Laguerre differential equation with the solution

W  z   Lqp p  z   L2nll11 z  (45)

The wavefunction of the Coulomb potential is now written as

2k 3 n  l  1! kr l 2l 1

nlm r , ,   e 2 kr  Lnl 1 2 kr Yl  ,  
m
(46)
2nn  l !3
Properties of the associated Laguerre polynomials:

Lqp  z    1q
dq
dz
L0
q pq
z  
p! dz p

e z z q d q p  q  z
z e 
e  zt 1t   p  q !3 
 

q 1
  t p Lqp  z   z p z q
e L p  z Lq
p' z   pp '
1  t  p 0 0 p!

zLqp1  z    p  q  1Lqp  z    p  1Lqp 1  z 

zLqp1  z    p  z Lqp  z    p  q Lqp 1  z 

Using these properties we can find all the wave-functions:

3 3
1 1  2 r
 1  2 r
R10 r   2   e ao 100 r , ,      e ao

 ao    ao 
 Table 1: Wave functions and their components

n m

1 0 0

2 0 0

2 1 0

2 1

3 0 0

3 1 0

3 1

3 2 0

3 2

3 2
Number of nodes equals n-l-1.
Number of nodes equals n-l-1.
The probability of finding an electron at the
nucleus (r = 0) is zero for all levels.
The probability for the electron to be further
from the nucleus increases for higher n.
 It is clear from the graphs, the wave functions of H-atom vanish at the origin
except for l=0 (S states). This means that the capture of the nucleus of an
atomic electron can occur only from a level with l=0.
The points at which the wave-function is zero are called nodes. The electron
has zero probability of being located at these nodes. In general the number of
nodes is n-l-1.
It is of great important to draw the radial probability density as a function of r.
from these graphs we conclude:
1-The radial probability distribution function indicates that the probability of
finding an electron at the nucleus (r = 0) is zero since the electron and nucleus
cannot occupy the same point in space at the same time.
2- We also see that higher principal quantum number orbitals have higher
probability of being further from the nucleus; they are less strongly bound and
can be further away.
Now if one calculate the expectation value of the position operator r he found
 1
3
3  ao
2r
 2 2
r 100    rr ddr   R10 rR10 r dr  4    r e dr
0  ao  0
 
n  ax n!
But  x e dx  n 1 , a 0, n is  ve integer
0 a
3
r 100  ao
2
In general it is easy to show that


2 2 1  l l  1 
r nlm   Rnl rRnl r dr  n ao 1  2 1  2  
0   n 
r 20 m  6ao r 30 m  13.5ao

Recall that the probability for finding the particle in the ground state at a
distance r from the origin is given by
3
 1  2  ao
2r
R10 r  r  4   r e
2 2
 ao 
Which is maximum at r=ao