The hydrogen atom and the

periodic table
4
I see the atoms, free and fine,
That bubble like a sparkling wine;
I hear the songs electrons sing,
Jumping from ring to outer ring;
Lister The Physicist

4.1 The hydrogen atom

Up to now we have been concerned with rather artificial problems. We said:
let us assume that the potential energy of our electron varies as a function of
distance this way or that way without specifying the actual physical mechanism
responsible for it. It was not a waste of time. It gave an opportunity of becoming
acquainted with Schrödinger’s equation, and of developing the first traces of a
physical picture based, perhaps paradoxically, on the mathematical solution.
It would, however, be nice to try our newly acquired technique on a more
physical situation where the potential is caused by the presence of some other
physical ‘object’. The simplest ‘object’ would be a proton, which, as we know,
becomes a hydrogen atom if joined by an electron.
We are going to ask the following questions: (i) What is the probability that
the electron is found at a distance r from the proton? (ii) What are the allowed
energy levels?
The answers are again provided by Schrödinger’s equation. All we have to
do is to put in the potential energy due to the presence of a proton and solve
the equation.
The wave function is a function of time, and one might want to solve prob-
lems, where the conditions are given at t = 0, and one is interested in the
temporal variation of the system. These problems are complicated and of little
general interest. What we should like to know is how a hydrogen atom behaves
on the average, and for that purpose the solution given in eqn (3.7) combined
with (3.11) is adequate. We may then forget about the temporal variation,
because
|w(t)|2 = 1, (4.1)
and solve eqn (3.13), the time-independent Schrödinger equation.
The proton, we know, is much heavier than the electron; so let us regard it as
infinitely heavy (that is immobile) and place it at the origin of our coordinate
system.
The potential energy of the electron at a distance, r, from the proton is
known from electrostatics:
e2
V (r) = – . (4.2)
4π 0 r
54 The hydrogen atom and the periodic table

Thus, the differential equation to be solved is

 2 
2 2 e
∇ ψ+ + E ψ = 0. (4.3)
2m 4π 0 r

It would be hard to imagine a physical configuration much simpler than that

of a proton and an electron, and yet it is difficult to solve the corresponding
differential equation. It is difficult because the 1/r term does not lend itself
readily to analytical solutions. Thanks to the arduous efforts of nineteenth-
century mathematicians, the general solution is known, but it would probably
mean very little to you. Unless you have a certain familiarity with the prop-
erties of associated Legendre functions, it will not make you much happier if
you learn that associated Legendre functions happen to be involved. So I will
not quote the general solution because that would be meaningless, nor shall I
derive it because that would be boring. But just to give an idea of the mathem-
atical operations needed, I shall show the derivation for the simplest possible
case, when the solution is spherically symmetric, and even then only for the
lowest energy.
z The potential energy of the electron depends only on the distance, r; it there-
fore seems advantageous to solve eqn (4.3) in the spherical coordinates r, θ , φ
(Fig. 4.1). If we restrict our attention to the spherically symmetrical case, when
r ψ depends neither on φ nor on θ but only on r, then we can transform eqn (4.3)
θ
without too much trouble. We shall need the following partial derivatives
y
φ ∂ψ ∂r ∂ψ
x = (4.4)
∂x ∂x ∂r
Fig. 4.1 and
Coordinate system used to transform  
eqn (4.3) to spherical coordinates. ∂ 2ψ ∂ ∂ψ ∂r
= . (4.5)
∂x 2 ∂x ∂r ∂x
When we differentiate eqn (4.5), we have to remember that ∂ψ/∂r is a function
of r and ∂r/∂x is still a function of x; therefore,
   
∂ ∂ψ ∂r ∂r ∂ ∂ψ ∂r ∂ψ ∂ 2 r
= +
∂x ∂r ∂x ∂x ∂r ∂r ∂x ∂r ∂x2
 
∂ 2 ψ ∂r 2 ∂ψ ∂ 2 r
= + . (4.6)
∂r2 ∂x ∂r ∂x2
Obtaining the derivatives with respect to y and z in an analogous manner,
we finally get

∂ 2ψ ∂ 2ψ ∂ 2ψ
∇ 2ψ = + 2 + 2
∂x2 ∂y ∂z
      
2
∂ ψ
2 ∂r ∂r 2 ∂r 2
= 2 + +
∂r ∂x ∂y ∂z
 2 
∂ψ ∂ r ∂ r ∂ r
2 2
+ + + . (4.7)
∂r ∂x2 ∂y2 ∂z2
 The hydrogen atom 55

We now have to work out the partial derivatives of r. Since

r = (x2 + y2 + z2 )1/2 , (4.8)

we get
∂r x
= 2 (4.9)
∂x (x + y + z2 )1/2
2

and
∂ 2r 1 x2
= 2 – 2 , (4.10)
∂x 2 2 2
(x + y + z ) 1/2 (x + y + z2 )3/2
2

and similar results for the derivatives by y and z. Substituting all of them in
eqn (4.7), we get
 
∂ 2ψ x2 y2 z2
∇ ψ= 2
2
+ +
∂r x2 + y2 + z2 x2 + y2 + z2 x2 + y2 + z2

∂ψ 3 x2
+ – (4.11)
∂r (x2 + y2 + z2 )1/2 (x2 + y2 + z2 )3/2

y2 z2 ∂ 2 ψ 2 ∂ψ
– 2 – = + .
(x + y2 + z2 )3/2 (x2 + y2 + z2 )3/2 ∂r2 r ∂r

Thus, for the spherically symmetrical case of the hydrogen atom the
Schrödinger equation takes the form,
   
2 ∂ 2 ψ 2 ∂ψ e2
+ + E+ ψ = 0. (4.12)
2m ∂r2 r ∂r 4π 0 r

It may be seen by inspection that a solution of this differential equation is

ψ = e–c0 r . (4.13)

The constant, c0 , can be determined by substituting eqn (4.13) in eqn (4.12)

 
2 2 e2
c20 e–c0 r + (–c0 e–c0 r ) + E + e–c0 r = 0. (4.14)
2m r 4π 0 r

The above equation must be valid for every value of r, that is the coefficient of
exp(–c0 r) and that of (1/r) exp(–c0 r) must vanish. This condition is satisfied if
2 c20
E=– (4.15)
2m
and
2 c0 e2
= . (4.16)
m 4π 0
From eqn (4.16),
e2 m
c0 = , (4.17)
4π 2 0
56
The negative sign of the energy
means only that the energy of this
state is below our chosen zero
point. [By writing the Coulomb
potential in the form of eqn (4.2)
we tacitly took the potential en-
ergy as zero when the electron is
at infinity.]
From experimental studies of the
spectrum of hydrogen it was
known, well before the develop-
ment of quantum mechanics, that
the lowest energy level of hydro-
gen must be –13.6 eV, and it was
a great success of Schrödinger’s
theory that the same figure could
be deduced from a respectable-
looking differential equation.
Niels Bohr, Nobel Prize, 1922.
The hydrogen atom and the periodic table
which substituted in eqn (4.15) gives
me4
E=– . (4.18)
802 h2
Thus, the wave function assumed in eqn (4.13) is a solution of the differential
equation (4.12), provided that c0 takes the value prescribed by eqn (4.17). Once
we have obtained the value of c0 , the energy is determined as well. It can take
only one single value satisfying eqn (4.18).
Let us work out now the energy obtained above numerically. Putting in the
constants, we get
(9.1 × 10–31 )(1.6 × 10–19 )4 kg C4
E=–
8(8.85 × 10–12 )2 (6.63 × 10–34 )2 F2 m–2 J2 s2
= –2.18 × 10–18 J. (4.19)
Expressed in joules, this number is rather small. Since in most of the sub-
sequent investigations this is the order of energy we shall be concerned with,
and since there is a strong human temptation to use numbers only between 0.01
and 100, we abandon with regret the SI unit of energy and use instead the elec-
tron volt, which is the energy of an electron when accelerated to 1 volt. Since
1 eV = 1.6 × 10–19 J, (4.20)
the above energy in the new unit comes to the more reasonable-looking
numerical value
E = –13.6 eV. (4.21)
What can we say about the electron’s position? As we have discussed many
times before, the probability that an electron can be found in an elementary
volume (at the point r, θ , φ) is proportional to |ψ|2 —in the present case it is
proportional to exp(–2c0 r). The highest probability is at the origin, and it de-
creases exponentially to zero as r tends to infinity. We could, however, ask a
slightly different question: what is the probability that the electron can be found
in the spherical shell between r and r + dr? Then, the probability distribution
is proportional to
r2 |ψ|2 = r2 e–2c0 r , (4.22)
which has now a maximum, as can be seen in Fig. 4.2. The numerical value of
the maximum can be determined by differentiating eqn (4.22)
d 2 –2c0 r
(r e ) = 0 = e–2c0 r (2r – 2c0 r2 ), (4.23)
dr
whence
1 4π 2 0
r= = = 0.0528 nm. (4.24)
c0 e2 m
This radius was again known in pre-quantum-mechanical times and was called
the radius of the first Bohr orbit, where electrons can orbit without radiating.
Thus, in quantum theory, the Bohr orbit appears as the most probable position
of the electron.
 The hydrogen atom 57

|ψ|2r2

Fig. 4.2
Plot of eqn (4.22) showing the
probability that an electron
(occupying the lowest energy state)
may be found in the spherical shell
0.0 0.8 1.6 2.4 rc0 between r and r + dr.

We have squeezed out about as much information from our one meagre
solution as is possible; we should look now at the other solutions which I shall
give without any proof. Sticking for the moment to the spherically symmetrical
case, the wave function is

ψn (r) = e–cn r Ln (r), (4.25)

where Ln is a polynomial, and the corresponding energies are (in electron

volts),

1
En = –13.6 , n = 1, 2, 3. . . . (4.26)
n2
The solution we obtained before was for n = 1. It gives the lowest energy,
and it is therefore usually referred to as the ground state.
If we have a large number of hydrogen atoms, most of them are in their
ground state but some of them will be in excited states, which are given by
n > 1. The probability distributions for the higher excited states have maxima
farther from the origin as shown in Fig. 4.3 for n = 1, 2, 3. This is fair enough;
for n > 1 the energy of the electron is nearer to zero, which is the energy of

|ψ|2r 2

n=1

Fig. 4.3
n=2 Plots of ψn2 r2 for the three lowest
n=3 energy (n = 1, 2, 3) spherically
symmetrical solutions. The curves are
normalized so that the total
probabilities (the area under curves)
0 2 4 6 8 10 12 14 16 18 20 rc0 are equal.