Coulomb Potential – Radial Equation

The Coulomb potential

Ze2 1
V (r) = − .
4π0 r
Schrödinger equation
h̄2 2
− ∇ ψ + V (r)ψ = Eψ
2m
Wave function
ψ(r, θ, φ) = R(r)Y (θ, φ)
Angular wave function
Ylm (θ, φ)
Radial equation " #
h̄2 d2 u Ze2 1 h̄2 l(l + 1)
− + − + u = Eu (1)
2m dr2 4π0 r 2m r2
where u(r) = rR(r).

The Coulomb potential admits continuum states (with E > 0), describing electron-proton
scattering, as well as discrete bound states, representing the hydrogen atom. Only the
latter will be considered here. We now proceed to solve Eq.(1).

We first try to tidy up the notations.

Divide both sides of the equation by 4E.

" #
h̄2 d2 u Ze2 1 h̄2 l(l + 1) 1
− 2
+ − + 2
u= u (2)
8mE dr 16π0 E r 8mE r 4
Rewrite the 2nd term such that
" #
h̄2 d2 u mZe2 h̄2 1 h̄2 l(l + 1) 1
− 2
+ − 2 + 2
u= u (3)
8mE dr 2π0h̄ 8mE r 8mE r 4
Define √
−8mE mZe2
α= , ρ = αr, β= (4)
h̄ 2π0h̄2 α
The dimension of α is 1/length, the new variable ρ is then dimensionless, β is also
dimensionless. In terms of α, β and ρ, the radial equation becomes
" #
1 d2 u mZe2 1 1 1 l(l + 1) 1
2 2
+ 2 2 − 2 2
u= u (5)
α dr 2π0h̄ α r α r 4
Or " #
d2 u β l(l + 1) 1
2
+ − 2
u= u (6)
dρ ρ ρ 4
Move all the u terms to the right hand side, we have
" #
d2 u 1 β l(l + 1)
2
= − + u (7)
dρ 4 ρ ρ2

This equation is identical to radial equation (1). We only changed some notations.

We now consider the asymptotic form at ρ → ∞.

One important technique in solving differential equation is to study the asymptotic form
of the equation. First of all, some terms in the the equation can be ignored when
the variable is very large or small. The equation is reduced to a simpler form and an
asymptotic behaviour of the solution can be easily obtained. We can then peel off this
asymptotic behaviour from the solution and concentrate on the remaining part which
must be finite in these limiting cases.

When ρ → ∞, the terms in 1/ρ and 1/ρ2 are much smaller compared to 1/4 and can be
neglected. Eq.(7) is approximately

d2 u 1
2
≈ u. (8)
dρ 4

The solution of Eq.(8) is

u(ρ) ≈ Ae−ρ/2 + Beρ/2.
However, the 2nd term will blow up when ρ → ∞. We must set B = 0. Therefore

u(ρ) ≈ Ae−ρ/2, (for ρ  1) (9)

Next, we consider the limit of ρ → 0.

When ρ → 0, the right hand side of Eq.(7) is dominated by the l(l + 1)/ρ2 term and the
equation is approximately
d2 u l(l + 1)
2
≈ u. (10)
dρ ρ2
Since the second derivative of u is proportional to ρ−2 u, a possible solution of this equation
is some power of ρ. Consider
u(r) = Cρk
du
= Ckρk−1
dρ
d2 u
= Ck(k − 1)ρk−2
dρ2
We need
k(k − 1) = l(l + 1)
This equation has two solutions

k = l + 1, and k = −l

and each gives an independent solution to Eq.(10). Therefore

u(r) = Cρl+1 + Dρ−l

However, we have to discard the second solution since it blows up as ρ → 0. The solution
for small ρ is therefore
u(ρ) = Cρl+1 , (for ρ  1) (11)

The next step is to peel off the asympotic behaviour and consider the general solution

Assume the general solution (valid for all ρ) is

u(ρ) = ρl+1 e−ρ/2 v(ρ) (12)

then v(ρ) must remain finite when ρ → 0 or ρ → ∞. We leave the normalization

constants to v(ρ).

We now determine v(ρ)

First, determine the equation satisfied by v(ρ). From Eq.(12),

!
du 1 dv l+1 1 dv
= (l + 1)ρl e−ρ/2 v − ρl+1 e−ρ/2 v + ρl+1 e−ρ/2 = − u + ρl+1 e−ρ/2
dρ 2 dρ ρ 2 dρ

!
d2 u l+1 l+1 1 du dv 1 dv d2 v
2
= − 2 u+ − + (l + 1)ρl e−ρ/2 − ρl+1 e−ρ/2 + ρl+1 e−ρ/2 2
dρ ρ ρ 2 dρ dρ 2 dρ dρ
!2 !
l+1 l+1 1 l + 1 1 l+1 −ρ/2 dv dv
= − 2 u+ − u+ − ρ e + (l + 1)ρl e−ρ/2
ρ ρ 2 ρ 2 dρ dρ
2
1 dv d v
− ρl+1 e−ρ/2 + ρl+1 e−ρ/2 2
2 dρ dρ
" # " #
2 2
(l + 1) l+1 l+1 1 2(l + 1) l+1 ρ/2 dv l+1 −ρ/2 d v
= − − + u + − 1 ρ e + ρ e
ρ2 ρ2 ρ 4 ρ dρ dρ2
" #
2
l(l + 1) l + 1 1 l+1 ρ/2 l ρ/2 dv l+1 −ρ/2 d v
= − + ρ e v + [2(l + 1) − ρ] ρ e +ρ e
ρ2 ρ 4 dρ dρ2

Substitute the above into Eq.(7), we get

d2 v dv
ρl+1 e−ρ/2 2
+ [2(l + 1) − ρ] ρl eρ/2 + [β − (l + 1)] ρl eρ/2v = 0
dρ dρ
Divide by ρl e−ρ/2

d2 v dv
ρ 2
+ [2(l + 1) − ρ] + [β − (l + 1)] v = 0 (13)
dρ dρ

This is the equation satisfied by v(ρ) and we must solve this equation to determine v(ρ).

Seeking for power series solution:

We assume that v(ρ) can be expressed as a power series in ρ:

∞
X
v(ρ) = a0 + a1ρ + a2ρ2 + · · · = aj ρj (14)
j=0

The derivatives of v(ρ) can then be calculated easilly.

X∞ X∞
dv
= a1 + 2a2 ρ + 3a3 ρ2 + · · · = jaj ρj−1 = (j + 1)aj+1 ρj
dρ j=1 j=0

∞ ∞
d2 v 2
X
j−2
X
2
= 2a2 + 6a3 ρ + 12a4 ρ + · · · = (j − 1)jaj ρ = j(j + 1)aj+1 ρj−1
dρ j=2 j=0

We have changed the dummy index j to get the last expresion in both of the above
equations, so that all terms contain ρj when we substitute these expressions into Eq.(13),
as shown below
∞
X ∞
X ∞
X ∞
X
j(j + 1)aj+1 ρj + 2(l + 1)(j + 1)aj+1 ρj − jaj ρj + (β − l − 1)aj ρj = 0
j=0 j=0 j=0 j=0

Or ∞
X
{[j(j + 1) + 2(l + 1)(j + 1)]aj+1 + (β − l − 1 − j)aj } ρj = 0
j=0

Equating the coefficients of like powers yields

(j + l + 1) − β
aj+1 = aj (15)
(j + 1)(j + 2l + 2)

This recursion formula determines the coefficients, and hence the function v(ρ). We start
with a0 = A, Eq.(15) gives us a1; from a1, we get a2, and so on. A becomes an overall
constant, to be fixed eventually by normalization of the wave function.

The power series must be truncated:

With the recursion formula (15), we obtained at least the power series of the solution.
However, there is still one problem. That is, the solution is not finite at large ρ if we
really keep all the terms (infinite) in the series. This can be seen from the following.
When j is large (terms involving large power of ρ),
aj+1 1
≈
aj j+1
Compare this with
∞ ∞
X xj X
ex = = bj xj
j=0 j! j=0

1 1 bj+1 1
bj+1 = , bj = , =⇒ =
(j + 1)! j! bj j+1
Thus, the high power terms in v(ρ) behave similarly as those in the expansion of eρ.
This means that when ρ → ∞, v(ρ) approaches ∞ in the same way as eρ . This does not
satisfy the requirement that v(ρ) must remain finite for all possible ρ values. The power
series must be truncated.

Keep terms upto the J th power in ρ, then

(J + l + 1) − β
aJ+1 = aJ = 0
(J + 1)(J + 2l + 2)
This requires that
β =J +l+1 (16)

Energy of the electron:

The allowed energies of the electron are determined from Eq.(16). Let

β =J +l+1≡n (17)

n is called the principal quantum number. From Eq.(4)

mZe2
β= =n
2π0h̄2 α
m2Z 2 e4 1 m2 Z 2e4 h̄2
2 4 2 = − 2 4 = n2
(2π0 ) h̄ α (2π0) h̄ 8mE
mZ 2e4 1
En = − 2 (18)
2(4π0) h̄ n2
2

From Eq.(17), n can be any positive integer, i.e., n = 1, 2, 3, · · ·.

Eq.(18) can be written as

Z2
En = Ry (19)
n2
where
me4
Ry = − = −13.6 eV (20)
2(4π0 )2h̄2
is called a Rydberg unit of energy.

Now the wave function:

We now try to construct the wave function. Consider first v(ρ). Since β = n, the
recursion formula (15) can be written as

(j + l + 1) − n
aj+1 = aj (21)
(j + 1)(j + 2l + 2)
From this, we can get
(n − l − 1)
a1 = − a0
1(2l + 2)
(n − l − 2) (n − l − 1)(n − l − 2)
a2 = − a1 = a0
2(2l + 3) 1 · 2 · (2l + 3)(2l + 2)
(n − l − 3) (n − l − 1)(n − l − 2)(n − l − 3)
a3 = − a2 = − a0
3(2l + 4) 3!(2l + 4)(2l + 3)(2l + 2)
For an arbitrary j,
(n − l − 1)(n − l − 2) · · · (n − l − j)
aj = (−1)j a0 (22)
j!(2l + j + 1)(2l + j) · · · (2l + 3)(2l + 2)
This can be written as
(n − l − 1)!(2l + 1)!
aj = (−1)j a0 (23)
j!(n − l − j − 1)!(2l + j + 1)!

v(ρ) can then be written as

n−l−1
X (n − l − 1)!(2l + 1)!
v(ρ) = a0 (−1)j ρj (24)
j=0 j!(n − l − j − 1)!(2l + j + 1)!

This can be converted to the Laguerre polynomial. The Laguerre polynomial is generally
written as (see for example, I. S. Gradshteyn and I. M. Ryzhik, Table of Integrals, Series,
and Products, Academic Press, 1980),
n
!
X n+µ xk
Lµn (x) = (−1) k
(25)
k=0
n−k k!

where !
p p(p − 1) · · · (p − n + 1)
=
n 1 · 2···n
and if both p and n are integers,
!
p p!
=
n n!(p − n)!
 n
! n
X n+m xk X (n + m)! xk
Lm
n (x) = (−1) k
= (−1)k (26)
k=0
n−k k! k=0 (m + k)!(n − k)! k!
Therefore
(n − l − 1)!(2l + 1)! n−l−1
X [(2l + 1) + (n − l − 1)]! ρj
v(ρ) = a0 (−1)j (27)
(n + l)! j=0 [(n − l − 1) − j]![(2l + 1) + j]! j!
which can be written as
v(ρ) = AL2l+1
n−l−1 (ρ) (28)
The prefactor is combined with a0 and renamed to A. A will be eventually determined
by the normalization condition of the radial wave function.

Putting the pieces together:

We have finally determined v(ρ) and therefore, we have completely determined the radial
function R(r). To put things together, we first note that v(ρ) is a function of ρ = αr,
where α can now be written as
mZe2 1
α=
2π0h̄2 n
This can be further written as
2Z 1
α= (29)
a0 n
where
4π0h̄2
a0 = = 0.529 × 10−10 m (30)
me2
is the Bohr radius. (Do not confuse this a0 with the constant term in the power series
expansion of v(ρ).)

Eq.(12) then gives

u(ρ) = Aρl+1 e−ρ/2 L2l+1
n−l−1 (ρ)
and    l    
1 2Zr 2Zr Zr 2Zr
Rnl (r) = u = A0 exp − L2l+1
n−l−1
r na0 na0 na0 na0
Finally apply the normalization condition
Z
|Rnl (r)|2 r2 dr = 1

A0 can be determined and is given by

v
u
u 2Z 3 (n − l − 1)!
A0 = t (31)
na0 2n(n + l)!
The complete normalized wave function is
v
u
u 2Z 3 (n − l − 1)! −Zr/na0 2Zr
 l 
2Zr

ψnlm (r, θ, φ) = t e L2l+1 Ylm (θ, φ). (32)
n−l−1
na0 2n(n + l)! na0 na0