Class 23: The hydrogen atom

The hydrogen atom contains a proton and an electron. Since the proton is much more massive than the
electron, it is reasonable approximation to treat the proton as being the fixed force center. However, it is
straightforward to allow for the finite mass of the proton by using a non-inertial frame of reference with
the proton at the origin. The Schrödinger equation for the motion of the electron relative to the proton is
then

ℏ 2  1 ∂  2 ∂ψ  1 ∂  ∂ψ  1 ∂ 2ψ  e2
− r + 2  sin θ +
 2 2 − k ψ = Eψ .
2µ  r 2 ∂r  ∂r 2 
(23.1)
 r sin θ ∂θ  ∂θ  r sin θ ∂φ  r

where k is a constant that depends on the choice of units. In cgs units, k = 1, and in SI units, k = 1 4πε 0 .
Also m has been replaced by the reduced mass

me m p
µ= = 0.999456me . (23.2)
me + m p

For the hydrogen atom, the radial function, R, is a solution of the equation

1 d  2 dR   1 2µ 2 1 2µ 
2 r  − l ( l + 1) 2 − 2 ke − 2 E  R = 0. (23.3)
r dr  dr   r ℏ r ℏ 

In terms of u = rR, this is

d 2u  1 2µ 1 2µ 
2
− l ( l + 1) 2 − 2 ke 2 − 2 E  u = 0. (23.4)
dr  r ℏ r ℏ 

We can find the behavior of the solution for large separation of electron and nucleus by dropping terms
proportional to inverse powers of r. This leads to

d 2R 2µ
2
= − 2 ER. (23.5)
dr ℏ

For the electron to be bound to the nucleus, the energy E is negative. The solution that goes to zero as r
goes to infinity is

R = e − ar , (23.6)

where the constant a is related to the energy by

2µ
a2 = − E. (23.7)
ℏ2

1
We can check to see if this is an exact solution by substituting it to equation (23.3). We find

2a  1 2µ 1 2µ 
a2 − − l ( l + 1) 2 − 2 ke 2 − 2 E  = 0. (23.8)
r  r ℏ r ℏ 

By inspecting the coefficients of terms that are powers of r, we see that l must be zero, i.e. the wave
function is spherically symmetric. Also we find

k µ e2 2 2µ
a= 2
, a = − 2 E. (23.9)
ℏ ℏ

By comparing with results from the Bohr model, we recognize a as the inverse of the Bohr radius, and E
as the ground state energy of the hydrogen atom. The normalized wave function for the ground state is

1
ψ 1,0,0 = 32
e − r a0 . (23.10)
π a0

The general solution for the wave function is

3
 2  ( n − l − 1) ! − r ( na0 )  2r  2 l +1  2r  m
l

ψ n ,l .m =   e   Ln −l −1   Yl (θ , φ ) , (23.11)
 na0  2n ( n + l ) !  na0   na0 

where L2nl−+l1−1 ( ρ ) is a generalized Laguerre polynomial of degree n – l – 1. Since the degree of the
polynomial must be greater than or equal to zero, we see that l is restricted to the range 0 ≤ l ≤ n − 1.

The energy eigenvalues are

1 k 2 µ e4
En = − . (23.12)
2n 2 ℏ 2

(These are the same as found from the Bohr model.) The energy depends only the principal quantum
number n, and not on the quantum numbers l and m. Hence for n > 0, there are a number of states with
the same energy. The number of these degenerate states for given n is

n −1 l n −1
wn = ∑ ∑ 1 = ∑ ( 2l + 1) = n 2 . (23.13)
l = 0 m =− l l =0

We shall find later than the electron can be in one of two intrinsic spin states. Hence the statistical weight
of a state of principal quantum number n is

g n = 2n2 . (23.14)

The hydeogen atom peobability densities

The general solution for the wave function is

2
  2  ( n − l − 1) ! − r ( na0 )  2r  2l +1  2r  m
3 l

ψ n ,l .m =   e   Ln −l −1   Yl (θ , φ ) , (23.15)
 na0  2n ( n + l ) !  na0   na0 

where Ln −l −1 ( ρ ) is a generalized Laguerre polynomial of degree n – l – 1. The angular dependencies

2l +1

have been combined into spherical harmonic functions

m 2l + 1 ( l − m ) ! m
Yl m (θ , φ ) = ( −1) Pl ( cos θ ) eimφ . (23.16)
4π ( l + m ) !

The figures below show gray scale plots of the probability density function for spherically symmetric
wave functions, i.e. l = 0. The length unit for each plot is na0 2.

5 5

4 4

3 3

2 2

1 1

0
z

0
z

-1 -1

-2 -2

-3 -3

-4 -4
n = 1, l = 0, m = 0 n = 2, l = 0, m = 0
-5 -5
-5 -4 -3 -2 -1 0 1 2 3 4 5 -5 -4 -3 -2 -1 0 1 2 3 4 5
x x

3
 5 5

4 4

3 3

2 2

1 1

0 0
z

z
-1 -1

-2 -2

-3 -3

-4 -4
n = 3, l = 0, m = 0 n = 4, l = 0, m = 0
-5 -5
-5 -4 -3 -2 -1 0 1 2 3 4 5 -5 -4 -3 -2 -1 0 1 2 3 4 5
x x

5
5
4
4
3
3
2
2
1
1
0
z

0
z

-1
-1
-2 -2

-3 -3

-4 -4
n = 5, l = 0, m = 0 n = 6, l =0, m = 0
-5 -5
-5 -4 -3 -2 -1 0 1 2 3 4 5 -5 -4 -3 -2 -1 0 1 2 3 4 5
x x

We see that as n increases, the number of dark rings where the probability density is extremely low also
increase. The number of dark rings, which correspond to spherical shells, is n – 1.

By integrating over the angular variables, we see that the probability that radial distance of the electron
from the proton is between r and r + dr is P ( r ) dr where

2l + 2 2
 2  ( n − l − 1) ! −2 r ( na0 )  2r 
3
 2 l +1  2r 
P (r ) =   e    Ln −l −1  na  . (23.17)
 na0  2n ( n + l ) !  na0    0 

The radial probability density is shown in the figure below for n = 1, 2, 3, 4, 5 and 6.

4
 0.6

n=1
n=2
n=3
n=4
0.4
n=5
n=6
|rψ |2

0.2

0.0

0 10 20 30 40 50 60 70 80 90 100
r

We see that as n increases, the most likely separation between the electron and proton also increases. The
most likely separation increases roughly as n2, as expected from the Bohr model.

The figures below are color plots of the probability densities for m = 0 and m =1 when n = 2, l = 1.

5 5 -9.000
-8.327
4 4 -7.654
-6.981
3 3
-6.308
-5.634
2 2
-4.961

1 1 -4.288
-3.615
0 0
z
z

-2.942
-2.269
-1 -1

-2 -2

-3 -3

-4 -4
n = 2, l = 1, m = 0 n = 2, l = 1, m = 1
-5 -5
-5 -4 -3 -2 -1 0 1 2 3 4 5 -5 -4 -3 -2 -1 0 1 2 3 4 5
x x

Remembering that the probability density distribution is azimuthally symmetric, we see that the l = 1, m =
1 distribution is doughnut shaped (toroidal), whereas the l = 1, m = 0 distribution has two symmetric
lobes.

The figures below show some probability distribution for n = 3.

5
 5 5

4 4

3 3

2 2

1 1

0 0

z
z

-1 -1

-2 -2

-3 -3

-4 -4
n = 3, l = 1, m = 0 n = 3, l = 1, m = 1
-5 -5
-5 -4 -3 -2 -1 0 1 2 3 4 5 -5 -4 -3 -2 -1 0 1 2 3 4 5
x x
5 5

4 4

3 3

2 2

1 1

0 0
z

-1 -1

-2 -2

-3 -3

-4 -4
n = 3, l = 2, m = 0 n = 3, l = 2, m = 1
-5 -5
-5 -4 -3 -2 -1 0 1 2 3 4 5 -5 -4 -3 -2 -1 0 1 2 3 4 5
x x

6
 5 -9.000
-8.420
4 -7.840
-7.260
3
-6.680
-6.100
2
-5.520

1 -4.940
-4.360
z 0 -3.780
-3.200
-1

-2

-3

-4
n = 3, l = 2, m = 2
-5
-5 -4 -3 -2 -1 0 1 2 3 4 5
x

Finally, here are a few n = 5 probability density distributions:

5 5 -10.00
-9.380
4 4 -8.760
-8.140
3 3
-7.520

2 -6.900
2
-6.280
1 1 -5.660
-5.040
0 0
z

-4.420
-3.800
-1 -1

-2 -2

-3 -3

-4 -4
n = 5, l = 3, m = 1 n = 5, l = 4, m = 0
-5 -5
-5 -4 -3 -2 -1 0 1 2 3 4 5 -5 -4 -3 -2 -1 0 1 2 3 4 5
x x

5 -8.500
-7.900
4 -7.300
-6.700
3
-6.100
-5.500
2
-4.900

1 -4.300
-3.700
0
z

-3.100
-2.500
-1

-2

-3

-4
n = 5, l = 1, m = 0
-5
-5 -4 -3 -2 -1 0 1 2 3 4 5
x

7
The radial probability functions are shown below for n = 3. We see that the radial distribution depends on
l but not m.

0.12

l = 0, m = 0
0.10 l = 1, m = 0
l = 1, m = 1
0.08 l = 2, m = 0
l = 2, m = 1

P(r) 0.06

0.04

0.02

0.00

0 10 20 30 40
r/a0

Connection to the Bohe model

The color plots of the probability distribution for quantum numbers l = m = n − 1 show a toroidal
distribution, which is suggestive of a classical circular orbit. The figure below is a plot of radial
probability distributions for n = 1, 2, 3, 4, 5 and l = m = n − 1.
1

n = 1, l = 0, m = 0
n = 2, l = 1, m = 1
n = 3, l = 2, m = 2
n = 4, l = 3, m = 3
n = 5, l = 4, m = 4
P(r)

0.1

0.01
0 10 20 30 40 50 60
r/a0

We see that the peak in the distribution is at radius r = n 2 a0 , which is the radius of the Bohr orbit for
principal quantum n. Since the hydrogen atom energies are independent of l and m, we see how the Bohr
model can give the correct energies.