PHY 314: Introduction to Quantum Mechanics, Varsha 2015

Lecture 17 and 18
Anil Shaji
School of Physics, IISER Thiruvananthapuram
The radial equation and the Hydrogen atom

We can now focus on the radial part of the three dimensional, time independent Schrodinger
equation,



d
2mr2 
2 dR
r

V (r) E R = l(l + 1)R.

2
dr
dr
~
Finding the solutions of this equation is a rather involved and lengthy process involving several
changes of variables and introducing new notation at many stages. Keeping track of all this takes
some effort. The strategy we will employ will be similar to the one we used in the case of the
quantum harmonic oscillator, where we looked at the asymptotic behavior of the equations and
then modified the asymptotic solution with a suitable function which had a series expansion.
The first change of variables we employ is


du
1
dR
du
dR
= r
u 2 r2
=r
u.
u rR;
dr
dr
r
dr
dr
The equation of interest can be rewritten in terms of u as
r


d2 u 2mr 
u
2 V (r) E u = l(l + 1) ,
2
dr
~
r

(1)

Multiplying both sides of the equation by r and rearranging terms we can rewrite the above equation
as


~2 l(l + 1)
~2 d2 u

+
V
+
u = Eu.
(2)
2m dr2
2m r2
This equation is called the radial equation and it is identical in form to the one dimensional, time
independent Schr
odinger equation with an effective potential given by
Veff = V +

~2 l(l + 1)
.
2m r2

The extra term, ~2 l(l + 1)/2mr2 is called the centrifugal term and just as in classical mechanics,
its effect is to push the particle away from the origin. To proceed further we have to specify the
central potential, V (r).

A.

The Hydrogen atom

The simplest of all atoms, Hydrogen, consists of a positively charges nucleus made up of a single
proton with an an electron bound to it. Since the proton is a thousand times more massive than

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the electron, we can assume that it is located at the origin of our coordinate system and that it
does not move. The potential that the electron feels dues to the proton is
V (r) =

1 e2
.
40 r

Putting this potential into the radial equation and using the substitution,

2mE
=
,
~
we get


me2 1
l(l + 1)
1 d2 u
u.
= 1
+
2 dr2
20 ~2 r
2 r2

(3)

Calling
r = ,

and

me2
= 0 ,
20 ~2

we simplify the equation to



0 l(l + 1)
d2 u
= 1
+
u.
d2

2
1.

(4)

Asymptotic behavior

Before trying to solve Eq. (4), let us look at the two limits, and 0. When ,
the constant term on the right side of Eq. (4) dominates and we get
d2 u
= u,
d2
which has the solution
u = Ae + Be .
Normalization requires that B = 0 and we have u = Ae . At the other extreme, when 0,
the 1/2 term dominates (when l 6= 0) and the radial equation reduces to
d2 u
l(l + 1)
=
u.
2
d
2
One solution to this equation is
u = Cl+1 +

D
.
l

But D/l blows up as 0 and so D = 0 if the solution is to be normalized.

Separating out the asymptotic solutions, one gets
u = e l+1 v()

(5)

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2.

Series solution

The equation for v is not all that simple, contrary to what we might have hoped for. We have
du
dv
= (l + 1)l e v l+1 e v + l+1 e
d
d


dv
,
= l e (l + 1 )v +
d
and
d2 u
= l e
d2





l(l + 1)
dv
d2 v
2l 2 + +
v + 2(l + 1 ) + 2 .

d
d

Substituting this into Eq. (4), we get


dv 
d2 v
+ 2(l + 1 ) + 0 2(l + 1) v = 0.
2
d
d

(6)

This does not look like a particularly simple equation to solve. But pressing on, we try a series
solution of the form
v() =

cj j .

j=0

We have to now find the coefficients c0 , c1 , . . .. We find

X
X
dv
=
jcj j1 =
(j + 1)cj+1 j
d
j=0

d2 v

d2

j=0

j(j + 1)cj+1 j1 .

j=0

Inserting these into Eq. (6), we get

j(j + 1)cj+1 j + 2(l + 1)

j=0

(j + 1)cj+1 j

j=0


X
jcj + 0 2(l + 1)
cj j = 0
j

j=0

j=0

Collecting the coefficients of like powers and equating them to zero (due to the uniqueness theorem),
we get


j(j + 1)cj+1 + 2(l + 1)(j + 1)cj+1 2jcj + 0 2(l + 1) cj = 0,
which implies that

2(j + l + 1) 0
cj .
=
(j + 1)(j + 2l + 1)


cj+1

(7)

Since this recursion relation connects cj+1 to cj , knowing c0 fixes everything else and c0 , in turn,
is determined by the normalization.

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Before evaluating the coefficients of the series solution, let us first look at the asymptotic
behavior of the series. When j is very large (compared to 0 and 1),
2
cj
j+1

cj+1 '
which leads to

2j
c0 .
j

cj =
Putting this into the series in (5),
v() = c0

X
2j
j=0

j = c0 e2

and so
u() = c0 l+1 e .
We see that u() blows up for large and furthermore, e is one of the solutions we actually got
rid of when we were looking at the asymptotic behavior of the equations. The solution where the
series does not terminate is indeed one possible solution of the radial equation except that it is not
the one we are looking for. The requirement that our wave functions be normalized means that we
require the series to terminate at some point. So there has to be jmax such that
cjmax +1 = 0
From the recursion relation in (7), the condition that must be satisfied for the series to terminate
is
2(jmax + l 1) 0 = 0.
Let us define
jmax + l 1 n,
where n is called the principal quantum number. Then
0 =
Using =

me2
= 2n.
20 ~2

2mE/~, we have
n2 =

me2
20 ~2

2 


~
.
2mE

The allowed energies are therefore labelled by n as


 2 2 
m
e
1
E1
En =
= 2,
2
2
2~ 40
n
n

n = 1, 2, . . .

(8)

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This is the formula originally derived by Niels Bohr in 1913 using a collection of ad-hoc assumptions
including the famous Bohr quantization condition.
The variable in our differential equation is = r and sets the typical scale of the wave
function because of the factor of e in the solution. Using the definition of 0 and the fact that
0 = 2n, we have


1
me2
1
=
=
,
2
40 ~ n
an
where
a

40 ~2
= 0.529 1010 m,
me2

is the Bohr radius. So we have

r
.
an
The radial wave function is labelled by two quantum numbers, n and l and we have
1
Rnl (r) = l+1 e v(),
(9)
r
and the full spatial wave function of the hydrogen atom is labelled by three quantum numbers (n,
l and m):
=

nlm (r, , ) = Rnl (r)Ylm (, ).

3.

(10)

The ground state

The ground state of the hydrogen atom corresponds to n = 1. The ground state energy is
 2 2
m
e
E1 = 2
= 13.6 eV = 21.79 1019 J.
2~ 40
Since n = jmax + l + 1, n = 1 means that l = 0 (and jmax = 0). So the ground state wave function
of hydrogen is
1
100 = R10 (r)Y00 (, ) = R10 (r).
4
When n = 1, the series for v() stops with j = 1 (c1 = 0). So we have
1
R10 (r) = (r)er c0 ,
r
and using = 1/a,
c0 r/a
e
.
a
Normalizing the radial wave function independently,
Z
Z
|c0 |2
a
dr r2 e2r/a = |c0 |2 = 1,
dr r2 |R(r)|2 = 2
a
4
0
0

and c0 = 2/ a. The ground state of the hydrogen atom is then

R10 (r) =

100 (r, , ) =

1
a3

er/a .

(11)

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4.

First excited state(s)

The next highest energy level of the Hydrogen atom is

E2 =

E1
= 3.4eV.
4

This energy corresponds to n = 2 and consistent with it there are four possibilities for the azimuthal
and magnetic quantum numbers, namely l = 0, m = 0 and l = 1, m = 1, 0, +1. When n = 2 and
l = 0,
c1 =

2(0 + 0 + 1 2)
c0 = c0
(0 + 1)(0 + 0 + 2)

using j = 0

and
c2 =

2(1 + 0 + 1 2)
c0 = 0
(1 + 1)(1 + 0 + 2)

using j = 1.

So we have


c0
r
R20 (r) =
1
er/2a .
2a
2a
When l = 1,
c1 =

2(0 + 1 + 1 2)
c0 = 0
(0 + 1)(0 + 2 + 2)

using j = 0,

and
R21 (r) =

c0 r/2a
re
.
4a2

The constant c0 , in each case, is determined by normalization. Using Y00 =



c0
r
200 =
1
er/2a ,
2a
8a
and using
r
Y10

3
cos ,
8

Y11

3
sin ei ,
8

we get
r
210 =

3 c0 r/2a
re
cos
8 4a2

and
r
211 =

3 c0 r/2a
re
sin ei .
8 4a2

p
1/4, we have

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5.

Other values of n

For any n, the possible values of l are

l = 0, 1, 2, . . . , n 1
because when l = n
cj+1 =

2(j + n + 1 n)
2
cj =
cj ,
(j + 1)(j + 2n + 2)
j + 2n + 2

which is a recursion relation that cannot terminate. For all values of l greater than n, the recursion
relation does not terminate either.
For each l, there are 2l + 1 possible values of m and so the number of states with energy En is
d(n) =

n1
X

(2l + 1) = n2 .

l=0

Apart from the normalization, c0 , the polynomial, v() defined by the recursion formula for cj
is known as the associated Laguerre polynomial,
v() = L2l+1
nl1 (2),
where
Lpqp (x) (1)p

d
dx

p
Lq (x).

The q th Laguerre polynomial, Lq (x) is, in turn, defined by

 q


x d
Lp (x) e
ex xq .
dx
Putting everything together, the normalized hydrogen atom wave functions are
s 
 
i
2 3 (n l 1)! r/na 2r l h 2l+1
nlm (r, , ) =
e
L
(2r/na)
Ylm (, ).
nl1
na 2n[(n + 1)!]3
na

(12)

Note that while the wave functions depend on all three quantum numbers, the energies depend
only on n. This is a peculiarity of the Coulomb potential. The wave functions are mutually
orthogonal,
Z

nlm
n0 l0 m0 r2 sin dr d d = nn0 ll0 )mm0 .

B.

The Hydrogen spectrum

Quantum mechanics really took off when the theoretical predictions matched the experimental
observations of the spectrum of Hydrogen. If we have a Hydrogen atom in isolation in some state,
that is not the lowest energy state, characterized by the three quantum numbers, n, l and m, it will

8
remain in that state. But the slightest disturbance the atom will undergo a transition (a change
of state) to the ground state. When the transition occurs, it will emit the excess energy,
E = En E1
as radiation. The atom can also absorb radiation and go from a lower state to a higher energy
state.
In general, when a transition occurs between energy levels Ei and Ef , the energy of the emitted
radiation will be


1
1
E1 E1
E = Ei Ef = 2 2 = (13.6 eV) 2 2 .
ni
nf
ni
nf
According to Plancks formula, the energy of the emitted radiation and its frequency is tied by
the relation
E = h.
The wave length of the emitted radiation is given by = c/ and so


1
1
1
=R 2 2

nf
ni
where
m
R=
4c~3

e2
40

2

= 1.097 107 m1 ,

is the Rydberg constant.

Transitions to the ground state all corresponds to ultraviolet radiation and these spectral lines
are called the Lyman series. The transitions to the first excited state correspond to visible radiation
and these spectral lines are called the Balmer series. Transitions to nf = 3 are the Paschen series
and these fall in the infra red part of the spectrum.