HYDROGEN ATOM

Vinesh Vijayan

1. Preface
Hydrogen atom has one electron and a proton. The proton is fixed at the origin and an
electron of reduced mass µ is interacting with the proton through a coulombic potential:

−e2
U (r) = (1)
4π0 r

2. Schrödinger equation
 2 2
∂2 ∂2
 
~ ∂
− + + + U (x, y, z) ψ = Eψ
2µ ∂x2 ∂y 2 ∂z 2
~2 ∂2 ∂2 ∂2
 
− + + ψ + U (x, y, z)ψ = Eψ
2µ ∂x2 ∂y 2 ∂z 2
 2
∂2 ∂2

2 ∂
Here ∇ = + +
∂x2 ∂y 2 ∂z 2
where ∇2 is called the Laplacian operator; Previous equation but now with ∇2 is :

~2 2
− ∇ ψ + [E − U (x, y, z)] ψ = 0
2µ
2µ
or ∇2 ψ + 2 [E − U (x, y, z)] ψ = 0
~
Since U (refer equation (1)) is a function of r ie. depends on the x, y and z coordinates,
separation of variables is very difficult in the Cartesian coordinate system. We therefore
resort to coordinate change from Cartesian to spherical co-ordinates. ie f (x, y, z) =
f (r, θ, φ). The Schrödinger equation of Hydrogen atom in spherical co-ordinate is:

∂ 2 ψ 2µ
   
1 ∂ 2 ∂ψ 1 ∂ ∂ψ 1
r + sin θ + + 2 (E − U (r)) ψ = 0 (2)
r2 ∂r ∂r r2 sin θ ∂θ ∂θ r2 sin2 θ ∂φ2 ~

Now we can try the separation of variable technique, by substituting ψ(r,θ,φ) = Rr Θθ Φφ

where R is the function of r only, Θ is the function of θ only and Φ is the function of φ
only. Substituting in Eq(2) we get:

∂ 2 (RΘΦ)
   
1 ∂ 2 ∂(RΘΦ) 1 ∂ ∂(RΘΦ) 1
r + sin θ +
r2 ∂r ∂r r2 sin θ ∂θ ∂θ r2 sin2 θ ∂φ2
2µ
+ 2 (E − U (r)) (RΘΦ) = 0
~ (3)
RΘ ∂ 2 Φ
  
ΘΦ ∂ 2 ∂R RΦ ∂ ∂Θ
r + 2 sin θ + 2 2
r2 ∂r ∂r r sin θ ∂θ ∂θ r sin θ ∂φ2
2µ
+ 2 (E − U (r)) (RΘΦ) = 0
~

1
Now dividing all through out by RΘΦ, Equation (3) becomes

∂2Φ
   
1 ∂ 2 ∂R 1 ∂ ∂Θ 1
r + sin θ +
(R)r2 ∂r ∂r (Θ)r2 sin θ ∂θ ∂θ (Φ)r2 sin2 θ ∂φ2 (4)
2µ
+ 2 (E − U (r)) = 0
~
We can now try isolating the φ part from the above equation. For this we need to
multiply Eq(4) all through out by r2 sin2 θ so that the third term of the above equation
is independent of θ and r . So now we get :

sin2 θ ∂ 1 ∂2Φ
   
2 ∂R sin θ ∂ ∂Θ
r + sin θ +
(R) ∂r ∂r (Θ) ∂θ ∂θ (Φ) ∂φ2
2µr2 sin2 θ
+ (E − U (r)) = 0
~2
(5)
sin2 θ ∂ 2µr2 sin2 θ
   
2 ∂R sin θ ∂ ∂Θ
r + sin θ + (E − U (r))
(R) ∂r ∂r (Θ) ∂θ ∂θ ~2
1 ∂2Φ
=−
(Φ) ∂φ2

3. Solutions of Φ
Equation 5 must hold for all values of the θ and φ and hence both sides must be equal
to a constant. Equating the right hand of the Equation(5) to m2 ; (a positive number
whose exact value is not known presently). We now have an equation in φ, which we can
try to solve. We have:

1 d2 Φ
− = m2
(Φ) dφ2
1 d2 Φ
so + m2 = 0
(Φ) dφ2
d2 Φ
+ Φm2 = 0
dφ2
Substituting Φ = eαx , the resulting auxiliary equation is

α2 + m2 = 0 or α = ±im

General solution would then be Φ = Am eimφ + A−m e−imφ . Here, the boundary condition
is Φ(φ + 2π) = Φ(φ). Note that φ varies from 0 to 2π. Applying the boundary condition
to the general solution of Φ:

Am eimφ + A−m e−imφ = Φ = Am eim(φ+2π) + A−m e−im(φ+2π)

= Am eimφ eim2π + A−m e−imφ e−im2π

In order for both the sides of the above equation to be equal we must have e±i2πm = 1 i.e
cos(2πm)±i sin(2πm) = 1. This is true only when m =0, ±1, ±2, . . . Since the boundary
condition imposes a positive and negative values for m, we can write the general solution
of Φ as:
Φm (φ) = Am eimφ where m = 0, ±1, ±2, . . . (6)

2
We can now normalize Φ and thereby obtain the value of Am . This can be achieved by
the following method:
Z 2π
Φ∗ Φdφ = 1
0
Z 2π
substituting Eq(6) we get A2m e−imφ eimφ dφ = 1
0
Z 2π
2
Am dφ = 1
0
1
∴ A2m = and hence
2π
1
Φm (φ) = √ eimφ
2π

4. Solutions of Θ
When the φ part of Equation(5) is replaced with m2 , Eq(5) becomes:

sin2 θ ∂ 2µr2 sin2 θ

   
2 ∂R sin θ ∂ ∂Θ
r + sin θ + (E − U (r)) = m2 (7)
(R) ∂r ∂r (Θ) ∂θ ∂θ ~2

Now we can isolate the θ and R part of the equation.

Dividing Eq(7) by sin2 θ through out makes the 1st and the last term of Eq(7) independent
of θ and 2nd term independent of r. Hence:

2µr2 m2
   
1 ∂ 2 ∂R 1 ∂ ∂Θ
r + sin θ + 2 (E − U (r)) = (8)
(R) ∂r ∂r (Θ) sin θ ∂θ ∂θ ~ sin2 θ
Collecting R and Θ terms on either sides, we get:

2µr2 m2
   
1 ∂ 2 ∂R 1 ∂ ∂Θ
r + 2 (E − U (r)) = − sin θ (9)
(R) ∂r ∂r ~ sin2 θ (Θ) sin θ ∂θ ∂θ

In Eq(9) the left hand side (LHS) have only r terms and right hand side (RHS) have
only θ terms. Let LHS = RHS = β, then for the Θ part we have:

m2
 
1 d dΘ
− sin θ =β (10)
sin2 θ (Θ) sin θ dθ dθ

and R equation is:

2µr2
 
1 d 2 dR
r + 2 (E − U (r)) = β (11)
(R) dr dr ~
At the moment we are going to concentrate on solving the Θ equation.
We have to first transform the Θ equation to a standard form that can be easily solvable.
This require the following manipulations on Eq(10).
Multiplying −Θ through out on Eq(10)

m2 Θ
 
1 d dΘ
sin θ − = −βΘ
sin θ dθ dθ sin2 θ
m2 Θ
 
1 d dΘ
or sin θ − + βΘ = 0
sin θ dθ dθ sin2 θ

3
Expanding the first term in the previous equation:

d2 Θ m2 Θ
 
1 dΘ
sin θ 2 + cos θ + βΘ − =0 (12)
sin θ dθ dθ sin2 θ

Our initial aim is to transform Eq(12) such that the equation is independent of sin and
dx
cos terms. For this let x = cos θ and ∴ = − sin θ . We also know that:
dθ

dΘ df (x) dx df (x) df (x)

= · = (− sin θ) = − sin θ (13)
dθ dx dθ dx dx
Now
d2 Θ
 
d df (x)
= − sin θ
dθ2 dθ dx
df (x) d df (x)
= − cos θ − sin θ ·
dx dθ dx
df (x) d dx df (x)
= − cos θ − sin θ · ·
dx dx
 dθ dx 
df (x) d df (x)
= − cos θ − sin θ − sin θ
dx dx dx

From the above equation, taking − sin θ outside the square brackets of the second term,
we get:
d2 Θ df (x) 2
2 d f (x)
= − cos θ + sin θ (14)
dθ2 dx dx2
dΘ d2 Θ
Now substituting dθ and dθ2
from Eq(13) and Eq(14) respectively in Eq(12), we get:
2
    
1 df (x) 2 d f (x) df (x)
sin θ − cos θ + sin θ + cos θ − sin θ
sin θ dx dx2 dx
2
m f (x)
+βf (x) − =0
sin2 θ
Expanding

df (x) d2 f (x) df (x) m2 f (x)

− cos θ + sin2 θ − cos θ + βf (x) − =0
dx dx2 dx sin2 θ
d2 f (x) df (x) m2 f (x)
sin2 θ − 2 cos θ + βf (x) − =0
dx2 dx sin2 θ
Since sin2 θ = 1 − cos2 θ, we can write the above equation in terms of only x and f (x)
as:
d2 f (x) df (x) m2 f (x)
(1 − x2 ) − 2x + βf (x) − =0 (15)
dx2 dx 1 − x2
Eq(15) is the well known Associated Legendre equation. Associated Legendre equa-
tion can be solved by the power series method. See section 5.

4
(i) Power series method of solution of differential equations
In particle in a box type of problems we encountered only second order differential equa-
tion with constant coefficient. We solved it in class by using the auxiliary equation.
However this is not a standard method of solving a second order differential equation.
General method of solution is by using a power series. Here we try to solve the following
differential equation (like the one in particle in a box) using the power series approach.
We have:
y 00 (x) + c2 y(x) = 0 where c2 > 0 (16)
Solution of y can be expanded in a power series about x=0. i.e
∞
X
y(x) = an xn = a0 + a1 x + a2 x2 + a3 x3 + . . .
n=0
∞
X
y 0 (x) = a1 + 2a2 x + 3a3 x3 + . . . = nan xn−1
n=1
∞
X
y 00 (x) = 2a2 + 3 · 2a3 x + . . . = n(n − 1)an xn−2
n=2

Substituting y 00 (x) and y(x) in Eq(16) we get:

∞
X ∞
X
n(n − 1)an xn−2 + c2 an xn = 0 (17)
n=2 n=0

Changing the summation index in the 1st term from n to k=n-2

∞
X
(k + 2)(k + 1)ak+2 xk
k=0

k is a dummy variable and hence the above summation can be written as:
∞
X
(n + 2)(n + 1)an+2 xn
n=0

Using this in Eq(17)

∞
X ∞
X
n 2
(n + 2)(n + 1)an+2 x + c an xn = 0
n=0 n=0
∞
X
(n + 2)(n + 1)an+2 + c2 an xn = 0
 
n=0

For the above equation to be true, the coefficient of xn should be zero. Hence

(n + 2)(n + 1)an+2 + c2 an = 0
c2
an+2 = − an
(n + 1)(n + 2)

This is a recursion relation that relates an coefficient to its an+1 coefficients. i.e if we
know a1 , we can find a3 , a5 etc. Similarly, knowing a0 , we can determine a2 , a4 etc.

5
Here we let a0 = A, and a1 = Bc Now, using the recursion relations we can determine
the rest of the coefficients.
c2 A c4 A
a0 = A, a2 = − , a4 = and
1·2 4·3·2·1
c2k A
∴ a2k = (−1)k where k = 0, 1, 2, . . .
2k!
c3 B c5 B c7 B
a1 = Bc, a3 = − , a5 = , a7 = − ,
3·2·1 5·4·3·2·1 7!
c2k+1 B
a(2k+1) = (−1)k where k = 0, 1, 2, . . .
(2k + 1)!
∞
X X∞ X∞
y= an xn = an xn + an xn
n=0 n=0,2,4,... n=1,3,5,...

Using the general form of the even and odd series in the above equation, we have
∞ ∞
X c2k x2k X c2k+1 x2k+1
y=A (−1)k +B (−1)k
2k! (2k + 1)!
k=0 k=0
The first term is the Maclaurin series for cos cx
and 2nd term is the Maclaurin series for sin cx
y = A cos cx + B sin cx

The expression that we obtained for y is the same result one obtain by using the auxiliary
equation method applied to the particle in a box problems

5. Powerseries solution to Associated Legendre equation

For clarity Associated Legendre equation (Eq(15) )that we obtained in section 4 is given
here:
d2 f (x) df (x) m2 f (x)
(1 − x2 ) − 2x + βf (x) − =0
dx2 dx 1 − x2
Here x = cos θ with cos θ varieng from 0 to π and hence x varies from 1 to -1. However
when x becomes 1 or -1 the above equation will have a singularity, i.e a general point
where a mathematical formula becomes undefined. In Eq(15) due to the (1 − x2 ) factor
in the denominator of the last term the singularity exist at 1 or -1. In order to remove
the singularity, f (x) has to be a function of (1 − x2 ). So we do the following substitution:

k
f (x) = 1 − x2 g(x) (18)

6
To find the value of k. We have from Eq(18):

k
f (x) = 1 − x2 g(x)
df (x)
k dg(x)
k−1
= 1 − x2 + k 1 − x2 × −2x × g(x)
dx dx

k dg(x)
k−1
= 1 − x2 − 2xk 1 − x2 g(x)
dx
d2 f (x)
 
d 2 k dg(x)

d h 2 k−1

i
= 1 − x − 2xk 1 − x g(x)
dx2 dx dx dx
2

2 k d g(x) 2 k−1 dg(x)

k−1
− 2k 1 − x2



= 1−x 2
− 2xk 1 − x g(x)
dx dx

2 2 k−2 2 k−1 dg(x)



−2x (k − 1) 1 − x g(x) + x 1 − x
dx
2

k d g(x)
k−1 dg(x) h
k−2
= 1 − x2 2
− 4xk 1 − x2 + 4kx2 (k − 1) 1 − x2
dx i dx
2 k−1


−2k 1 − x g(x)

df (x) d2 f (x)
Substituting the values of f (x), dx and dx2
in Eq(15):

k+1 d2 g(x) 2 k dg(x)
h
2 k−1

i
2 k
1 − x2 2



2
− 4xk 1 − x + 4kx (k − 1) 1 − x − 2k 1 − x g(x)
dx dx
m2
   

k dg(x)
k−1
k
−2x 1 − x2 − 2xk 1 − x2 g(x) + β − 2
1 − x2 g(x) = 0
dx 1−x

k+1 d2 g(x)
k dg(x)
k−1 
1 − x2 − 2x 1 − x2 (2k + 1) + 4kx2 1 − x2

2
(k − 1
) + 1
g(x)
dx dx
h
2 k

k
k−1 i
g(x) + β 1 − x2 − m2 1 − x2


−2k 1 − x g(x) = 0

Now collecting the terms with same powers of 1 − x2 we have:

2
 
2 k+1 d g(x) 2 k dg(x)



1−x + 1−x β − 2x(2k + 1) − 2k
dx2 dx

k−1  2 2
+ 1 − x2 4x k − m2 g(x) = 0


k
Dividing by 1 − x2 through out:

d2 g(x)
 
dg(x)
1 − x2 + (β − 2k)g(x) + 2x(2k + 1)
dx2 dx
−1
+ 1 − x2 4x2 k 2 − m2 g(x) = 0

 

So far so good. But because of the last term, there still exist a singularity at x = ±1. In
order for the last term to disappear at x = ±1 the coefficient of the last term should go
to zero. This is possible when:
4k 2 − m2 = 0
4k 2 = m2
m2
k2 =
4
|m|
k=
2

7
 |m|
Now we have no singularity if k = 2 . Hence Eq(18) becomes

|m|
f (x) = 1 − x2 2
g(x) (19)
We have to take the derivative and its double derivatives of Eq(19) for substitution into
Eq(15), so:
df (x)
|m| dg(x) |m|
|m| −1
= 1 − x2 2
+ 1 − x2 2 × −2x × g(x)
dx dx 2

|m| dg(x) |m|
|m| −1
= 1 − x2 2 − 2
x 1 − x2 2 g(x)
dx 2


|m| dg(x)
|m| −1
= 1 − x2 2 − |m|x 1 − x2 2 g(x)
dx
d2 f (x)
   
d
|m|
2 2 dg(x) d
|m|
2 2 −1
= 1−x − |m|x 1 − x g(x)
dx2 dx dx dx

|m| 2

2 2 d g(x) |m|
|m|
2 2 −1 dg(x)

|m|
2 2 −1
= 1−x − 2 x 1 − x − |m| 1 − x g(x)
dx2


2
dx

|m|
|m| −2
|m| −1 dg(x)
−2x2 ( − 1) 1 − x2 2 g(x) + x 1 − x2 2
2 dx
|m| 2
d g(x) |m|
|m|
2 2 −1 dg(x) 2 2 −1
1 − x2 2



= − |m|x 1 − x − |m| 1 − x g(x)
dx2 dx
|m|
|m| −2
|m| −1 dg(x)
+2x2 |m|( − 1) 1 − x2 2 g(x) − |m|x 1 − x2 2
2 dx
dg(x)
Grouping
dx
|m|
d2 g(x)
|m|
2 2 −1 dg(x)
1 − x2 2


= − 2|m|x 1 − x
dx2   dx
|m|
x 2
−1
−|m| 1 − x2 2


1− (|m| − 2) g(x)
1 − x2
df (x) d2 f (x)
Now substituting dx and dx2
from the above equation in Eq(15) we get:

|m| d2 g(x)


|m|
2 2 −1 dg(x)
0 = (1 − x2 ) 1 − x2
2
− 2|m|x 1 − x
dx2 dx
2
|m|
   
−1 x
|m|
2 2 dg(x)
−|m| 1 − x2 2


1− (|m| − 2) g(x) − 2x 1 − x
1 − x2 dx
|m|
 |m| |m|

−1
−1
−|m|x 1 − x2 2 g(x) + β 1 − x2 2 g(x) − |m|2 1 − x2 2


g(x)

|m| +1 d2 g(x)
|m|

2 2 dg(x)
= 1 − x2
2
− 2|m|x 1 − x
dx2 dx
2
|m|

x
|m|
2 2 dg(x)
−|m| 1 − x2 2 1 −


(|m| − 2) g(x) − 2x 1 − x
1 − x2 dx
|m| |m| |m|
−1 −1
+2|m|x2 1 − x2 2 g(x) + β 1 − x2 2 g(x) − |m|2 1 − x2 2




g(x)

|m|
Dividing by 1 − x2 2
through out:

d2 g(x) x2
 
2 dg(x) dg(x)
0 = 1−x 2
− 2|m|x − |m| 1 − 2
(|m| − 2) g(x) − 2x
dx dx 1−x dx
2|m|x 2 |m|2
+ 2
g(x) + β g(x) − g(x)
1−x 1 − x2

8
 dg(x)
Collecting dx terms:

d2 g(x) x2 2|m|x2
 
2 dg(x)
0 = 1−x − 2(|m| + 1)x − |m| 1 − (|m| − 2) g(x) + g(x)
dx2 dx 1 − x2 1 − x2
|m|2
+β g(x) − g(x)
1 − x2
m
Taking 1−x2
common from the 3rd, 4th and 6th term of the above expression:

d2 g(x)
 
2 dg(x) |m| 2 2 2 2
0 = 1−x − 2(|m| + 1)x − 1 − x − x |m| +  2x − 
 2x + |m| g(x)

dx2 dx 1 − x2
+β g(x)

2
 
2 d g(x) dg(x) |m| 2 2
= 1−x − 2(|m| + 1)x − (1 − x ) + (1 − x )|m| g(x) + β g(x)
dx2 dx 1 − x2

Now expanding the terms in the above expression :

d2 g(x) dg(x)  
1 − x2 − 2(|m| + 1)x + β − |m|(1 + |m|) g(x) = 0 (20)
dx2 dx

Eq(20) can be solved by the power series method.

We now try expanding g(x) as a power series.
∞
X
g(x) = an xn
n=0
∞ ∞
dg(x) X X
= nan xn−1 = (n + 1)an+1 xn
g(x)
n=1 n=0
∞ ∞
d2 g(x) X X
= n(n − 1)an xn−2 = (n + 2)(n + 1)an+2 xn
dx2
n=2 n=0

Substituting the above expressions in Eq(20)

∞
X ∞
X
(1 − x2 ) (n + 2)(n + 1)an+2 xn − 2(|m| + 1)x (n + 1)an+1 xn
n=0 n=0
 ∞
X
+ β − |m|(1 + |m|) an xn = 0
n=0
∞
X ∞
X ∞
X
(n + 2)(n + 1)an+2 xn − x2 (n + 2)(n + 1)an+2 xn − 2(|m| + 1)x (n + 1)an+1 xn
n=0 n=0 n=0
 ∞
X
+ β − |m|(1 + |m|) an xn = 0
n=0
∞
X ∞
X ∞
X
(n + 2)(n + 1)an+2 xn − (n + 2)(n + 1)an+2 xn+2 − 2(|m| + 1) (n + 1)an+1 xn+1
n=0 n=0 n=0
 ∞
X
+ β − |m|(1 + |m|) an xn = 0
n=0

9
The second and third term in the above expression can be written as
∞
X ∞
X
n+2
(n + 2)(n + 1)an+2 x = n(n − 1)an xn and
n=0 n=0
∞
X X∞
(n + 1)an+1 xn+1 = nan xn
n=0 n=0

Here we have used the idea that if we replace n by n0 + 2 (n0 + 1 for the 3rd term) in
the LHS we still get back the RHS. Since n0 is a dummy variable we could replace the
original n. (NOTE: Understand that the first term of the summation on either side is
the same). When we substitute the RHS in the differential equation we get:
∞
X ∞
X ∞
X
(n + 2)(n + 1)an+2 xn − n(n − 1)an xn − 2(|m| + 1) nan xn
n=0 n=0 n=0
 ∞
X
+ β − |m|(1 + |m|) an xn = 0
n=0
∞
X ∞
X
(n + 2)(n + 1)an+2 xn + − n2 + n − 2|m|n − 2n + β − m2 − |m| an xn = 0
 
n=0 n=0
∞
!
X
(n + 2)(n + 1)an+2 + − n2 + 
n − 2|m|n − 2
n + β − m2 − |m| an xn = 0
 
n=0

In order for the above equation to go to zero, coefficients of xn should go to zero. There-
fore:
n2 + n + 2|m|n − β + m2 + |m|
an+2 = an
(n + 2)(n + 1)
We can now factorize the numerator to obtain the recursion formula.
(n + |m|)(n + |m| + 1) − β
an+2 = an (21)
(n + 2)(n + 1)

The general solution is an arbitrary linear combination of series of odd powers (a1 will
determine the coefficient of the series) and series of even powers (a0 will determine the
coefficients). However the infinite series does not converge and diverges at x = ±1.
NOTE:
∞
X 1
xn = only when |x| < 1 and diverges if |x| ≥ 1
1−x
n=0
Since x can take ±1, the general solution that we calculated is not a proper wave function
for the Hamiltonian. We can eliminate one of the series if we take the first coefficient
in the series to be zero ( i.e taking either a1 or a0 to be 0), but still the function will
diverge because of the other series. Hence the odd or the even series need to be truncated
at a particular value of n. This is possible if at a particular value of n the numerator
disapears in the recursion formula. Lets say that this happens at n = k then:
(k + |m|)(k + |m| + 1) = β where k = 0, 1, 2, 3, . . .
Since |m| can only take 0, 1, 2, . . . etc., k + |m| can also only take 0, 1, 2, . . .. We define
another quantum number l = k + |m|, the above equation becomes:

l(l + 1) = β (22)

10

|m|
Now, knowing x = cos θ and by Eq(19), the wave function f (x) = 1 − x2 2
g(x) and
g(x) = kn=0,2,4,... an xn , we can write the wave function Θ:
P
n=1,3,5,...

l−|m|
X
|m|
Θl,m = sin θ an cosn θ (23)
n=0,2,4,...
n=1,3,5,...

Here l and m are angular momentum quantum number and magnetic quantum number
respectively, and n is just a running variable for the indices of cos θ and a. Weather we
have odd or even series is determined by the value of l − |m| being odd or even. Hence
according to Eq(22), l ≥ |m|. For a given l, the possible values of m is: m = −l, −l +
1, . . . , 0, . . . , l + 1, l. Hence there are 2l + 1, m values for a given l. The summation series
in Eq(23) is actually the associated Legendre polynomial in cos θ and can be generated
using standard equation (see text book Quantum Chemistry by McQuarrie).
The Θ and Φ part of the wave function can be grouped together and describe the angular
part of the total wave function. The grouping is called the spherical harmonics and is
represented by Ylm (θ, φ)

Ylm (θ, φ) = Θl,m Φm

l−|m|
X
Ylm (θ, φ) = A sin θ|m| eimφ an cosn θ (24)
n=0,2,4,...
n=1,3,5,...

Where A is the normalization constant

6. Solutions of radial equation

Remembering equation 11
2µr2
 
1 d 2 dR
r + 2 (E − U (r)) = β
(R) dr dr ~
We now substitute the value of β obtained from the last section. Eq(11) becomes:

2µr2
 
1 d 2 dR
r + 2 (E − U (r)) = l(l + 1) (25)
(R) dr dr ~
Expanding the brackets and re-arranging:
2µr2
 
d 2 dR
r + 2 (E − U (r)) R − l(l + 1)R = 0
dr dr ~
2
d R dR 2µr2
r2 2 + 2r + 2 (E − U (r)) R − l(l + 1)R = 0
dr dr ~
2 2 Ze2

2d R dR 2µr
r + 2r + 2 E+ R − l(l + 1)R = 0
dr2 dr ~ 4π0 r
where we have used the value of U (x) from Eq(1). Here the Ze is the charge on the
nucleus. We substitute e0 = e2 /(4π0 )1/2 . This makes the previous equation:

d2 R dR 2µr2 Ze02
 
r2 2 + 2r + 2 E+ R − l(l + 1)R = 0 (26)
dr dr ~ r

11
Now we do the following substitution; y(r) ≡ rR; This would get rid of the first
derivative from the above equation.
y(r) ≡ rR; R = y/r;
dR y 1 dy
=− 2 +
dr r r dr
d2 R d dR 2y 1 dy 1 dy 1 d2 y
= = 3 − 2 − +
dr2 dr dr r r dr r2 dr r dr2
or
d2 R 1 d2 y 2 dy 2y
2
= 2
− 2 + 3
dr r dr r dr r
2
Now replacing the above expression for ddrR2 and dR
dr in Eq(26), we get:
Ze02 y
 2
2µr2
    
1d y 2 dy 2y y 1 dy y
r2 − + + 2r − + + E + − l(l + 1) = 0
r dr2 r2 dr r3 r2 r dr ~2 r r r
Expanding the brackets, we get:
d2 y Ze02
 
dy 2y 2y dy 2µr y
r 2 −2 + − +2 + 2 E + y − l(l + 1) = 0
dr dr r r dr ~ r r
2 02
 
d y 2µr Ze y
r 2 + 2 E+ y − l(l + 1) = 0
dr ~ r r

Now dividing by r through out:

d2 y 2µ Ze02
 
y
+ 2 E+ y − l(l + 1) =0 (27)
dr2 ~ r r2
 2
= − 2µE


Now we substitute 2 ~2
, for making the equation combat:
2 2µEZe02 2 l(l + 1)
 
d y
+ − − y=0
dr2 ~2 r 4 r2
We make another substitution here that relate radial distance (r) to energy().
ρ ≡ r (28)
ρ dp
r = ; dr =
 
d2 y d dy
= ;
dr2 dr dr
Now substituting for dr from above equation
d2 y d dy 2
2d y
=   =  (29)
dr2 dρ dρ dρ2
Using Eq(29) we could re-write the radial equation in terms of y being function of ρ as:
2 2µZe02 2 2 l(l + 1)
 
2d y
 + − − y=0
dρ2 ρ~2 4 ρ2
Dividing by 2 through out:
d2 y 2µZe02 1 l(l + 1)
 
+ − − y=0 (30)
dρ2 ρ~2 4 ρ2
Equation (30) is the equation we need to solve. First we try to find the Asymptotic
solution i.e solution of y when r( here ρ) is at the extreme (r or ρ → 0 and ∞)

12
(i) Asymptotic solution to radial equation
We will have two cases
1. When ρ → ∞.
In this case the terms in Equation(30) which have ρ in the denominator go to zero. Hence
Eq(30) becomes
d2 y 1
− y=0
dρ2 4
d2 y 1
2
= y
dρ 4

Using the trial function y = eαρ we have:

1
α2 =
4
1
α=±
2

The general solution under the circumstances would be:

y = C1 e−ρ/2 + C2 eρ/2
C2 has to be zero to prevent the solution of y blowing up at very large ρ. Hence we are
left with the first term in the general solution:
y = C1 e−ρ/2 (31)
2. When ρ → 0 In this case the term with ρ2 will be the most dominant term in the
expression of Eq(30). We then have:
d2 y l(l + 1)
− y=0
dρ2 ρ2

This equation can be solved by assuming a trial function y = ρk . Our aim is then to find
the value of k.
Substituting the trial function in the above equation, we have:
k(k − 1)ρk−2 − l(l + 1)ρ−2 ρk = 0
k(k − 1)ρk−2 − l(l + 1)ρk−2 = 0
∴ k(k − 1) − l(l + 1) = 0
k 2 − k − l(l + 1) = 0
p
1 ± 1 + 4(l(l + 1))
k=
√2
1 ± 1 + 4l2 + 4l
k=
p2
1 ± (2l + 1)2
k=
2
1 ± (2l + 1)
k=
2
∴ k = −l & k = l + 1

13
General solution would be:
y = C3 ρ−l + C4 ρl+1
Here again C3 has to be zero since as ρ → 0 the first term in the above expression
becomes undetermined. Hence
y = C4 ρl+1 (32)

7. Power series method of solution

Taking care of the asymptotic behavior we could write the general form of y as :
y = Cρl+1 e−ρ/2 υ(ρ) (33)
d2 y
Finding dρ2
:

y = Cρl+1 e−ρ/2 υ(ρ)

ρl+1 −ρ/2
 
dy dυ
= C (l + 1)ρl eρ/2 υ − e + ρl+1 e−ρ/2
dρ 2 dρ
"
d2 y l + 1 l −ρ/2 dυ
2
= C l(l + 1)ρl−1 e−ρ/2 υ − ρe υ + (l + 1)ρl e−ρ/2 −
dρ 2 dρ
l + 1 l −ρ/2 ρl+1 −ρ/2 ρl+1 −ρ/2 dυ dυ
ρe υ+ e υ− e + (l + 1)ρl e−ρ/2 −
2 4 2 dρ dρ
#
ρl+1 −ρ/2 dυ 2
l+1 −ρ/2 d υ
e +ρ e
2 dρ dρ2
Collecting similar terms:
"
d2 y l−1 −ρ/2 l −ρ/2 l −ρ/2 dυ ρl+1 −ρ/2
= C l(l + 1)ρ e υ − (l + 1)ρ e υ + 2(l + 1)ρ e + e υ−
dρ2 dρ 4
#
2
l+1 −ρ/2 dυ l+1 −ρ/2 d υ
ρ e +ρ e
dρ dρ2

Now substituting in Eq(30)

"
ρl+1 −ρ/2

C l(l + 1)ρ l−1 −ρ/2
e υ − (l + 1)ρ 
e l −ρ/2

υ + 2(l + 1)ρ 
e dυ
l −ρ/2
+  e

υ−
dρ 4
# 
2υ 2µZe02 1 l(l + 1)

l+1 −ρ/2 dυ l+1 −ρ/2 d
e−ρ/2
Cρl+1
  υ = 0
ρ  e  +ρ  e 
2
+ 2
− − 
2
dρ dρ ρ~ 4 ρ
After cancelling all common terms:
dυ dυ d2 υ
l(l + 1)ρl−1 υ − (l + 1)ρl υ + 2(l + 1)ρl − ρl+1 + ρl+1 2 +
dρ dρ dρ
2µZe02 l
ρ υ − l(l + 1)ρl−1 υ = 0
~2
Dividing by ρl through out:
d2 υ 2µZe02
 
dυ dυ
ρ 2 + 2(l + 1) −ρ + −l−1 υ =0
dρ dρ dρ ~2

14
Collecting the terms:

d2 υ 2µZe02
 
dυ
ρ 2 + (2(l + 1) − ρ) + −l−1 υ =0 (34)
dρ dρ ~2

Now we use the power series method for the solution of υ:

∞
X
υ= aj ρj
j=0
∞ ∞
dυ X X
= jaj ρj−1 = (j + 1)aj+1 ρj
dρ
j=0 j=0
∞
d2 υ X
= j(j − 1)aj ρj−2
dρ2
j=0
∞ ∞
d2 υ X X
ρ = j(j − 1)aj ρj−1 = (j + 1)jaj+1 ρj
dρ2
j=0 j=0

Substituting these in Eq(34)

∞ ∞ ∞ ∞
2µZe02
X X X X 
j j j
(j + 1)jaj+1 ρ + 2(l + 1) (j + 1)aj+1 ρ − jaj ρ + − l − 1 aj ρj = 0
~2
j=0 j=0 j=0 j=0
∞  02
 !
X 2µZe
[j(j + 1) + (2l + 1)(j + 1)] aj+1 + − l − 1 − j aj ρj = 0
~2
j=0

In order for the equation to go to zero, the coefficient of ρj should go to zero.

This is possible if:
2µZe02
 
(j + 1)(j + 2l + 1)aj+1 = j+l+1− aj
~2

We then have the recursion formula:

 
2µZe02
j+l+1− ~2
aj+1 = aj (35)
(j + 1)(j + 2l + 1)

Hence knowing the initial constant (a0 ) we can determine the rest of the series.
P∞ However
we do not yet know if the solution of y (Eq(33)) including the infinite series( j=0 aj ρj )
is a well behaved function. In order to understand its behavior for large values of r or ρ,
we first look at the infinite series.
Since for large ρ higher powers dominate and so we simply look at large values of j in
the ratio of coefficients. Using Eq(35) at large values of j we have:
aj+1 j 1
= =
aj (j + 1)j j+1

15
However, we can see below that the behavior of the coefficients at large values of j is
similar to the behavior of the coefficients in the series expansion of eρ ;
∞
X ρj
eρ =
j!
j=0

Taking the ratio of coefficient of j + 1 and j term in the above expansion, we have:
aj+1 1 j! 1
= × =
aj (j + 1)! 1 j+1
We can now clearly see that the infinite series given by the recursion formula will behave
just like eρ at large values of j.
Now let us look at the full solution of y:
∞
X
y = Cρl+1 e−ρ/2 aj ρj
j=0

We already know that at large ρ values the infinite series will behave like eρ so:
y = Cρl+1 e−ρ/2 eρ = Cρl+1 eρ/2

Because of the eρ/2 in the solution of y the function definitely will not go to zero at
ρ → ∞. Hence we need to terminate the power series and prevent it from running to
∞. This is possible if we set the numerator of the recursion formula (Eq(35) to zero.
Truncating the power series at j = k:
2µZe02
k+l+1− =0
~2
2µZe02
k+l+1= (36)
~2
Since k can take values 0, 1, 2, 3, . . ., we could write a new quantum number n = k + l + 1.
Since k and l are all positive values and have a minimum value of zero, n can only take
values n = 1, 2, 3, . . .. n is called the principle quantum number
Substituting n in Eq36:
2µZe02
n=
~2
4µ Z 2 e04
2
n2 =
2 ~4
  2 2µE
Remembering the value = − 2 we have:
2 ~
µ 2 Z 2 e04
n2 = − 2µE
~2
~4
µZ 2 e04
n2 = −
2E~2
µZ 2 e04
∴E=− 2 2
2n ~
0 2 1/2
Substituting now e = e /(4π0 ) and ~ = h/2π expression of Energy would be:
µZ 2 e4
E=−
820 n2 h2
(37)

16
The radial wave function would be :
n−l−1
X
l+1 −ρ/2
y = Cρ e aj ρj (38)
j=0

Remembering:

ρ = r
2 2µE
=− 2
4 ~
2 e4
32π 2 µE 32π 2 µ 8µZ
2 n2 h2
2 = − = 0
h2 h2
where we substituted the value of E from Eq(37)
32π 2 µ2 e4
2 =
8h4 20 n2
2πµe2 2 πµe2
= 2 =
h 0 n n h2 0
2
=
na0
h2 0
where we have used bohr radius a0 = . Hence:
πµe2
2r
ρ=
na0

Substituting the value of ρ in Eq(38), we get:

 l+1 n−l−1  j
2r r
− na
X 2r
y=C e 0 aj
na0 na0
j=0
 l+1 n−l−1  j
2 r
l+1 − na0
X 2r
y=C r e aj (39)
na0 na0
j=0

Finally remembering that R = y/r we have from previous equation Eq(39), the radial
function, R will have the form:

 l+1 n−l−1  j
2 r
l − na0
X 2r
R(r) = y/r = C re aj (40)
na0 na0
j=0

The summation series in the above equation actually turns out to be the Laguerre poly-
nomials and can be easily generated using standard formula.
Total wave function of Hydrogen atom:

ψn,l,m (r, θ, φ) = Rn,l (r)Ylm (θ, φ) (41)

17