Bohr’s atomic model

Another interesting success of the so-called old quantum theory is explaining atomic
spectra of hydrogen and hydrogen-like atoms. The electromagnetic radiation emitted
by free atoms is concentrated at a number of discrete wavelengths. Each kind of atom
has its own characteristic spectrum i.e. a different set of wavelengths at which the
lines of the spectrum are found. To explain the discrete nature of the spectral lines,
Bohr postulated (1913)

1. Electron in an atom moves in circular orbits, obeying classical mechanics, about

the nucleus under Coulomb interaction thus obeying classical electromagnetic
theory.

2. Of all the infinite set of orbits possible in classical mechanics, electron moves
only in those for which its orbital angular momentum is an integral multiple
of h/2π, i.e. L = n~, which is a departure from classical mechanics. Fur-
ther, electron moving in such an orbit does not loose energy by electromagnetic
radiation, though it is in accelerated motion, thereby defying classical electro-
magnetic theory on the way.

3. Electromagnetic radiation is emitted if electron, initially moving in an orbit

with energy Ei , jumps discontinuously to another orbit of energy Ef and the
frequency of the emitted radiation is ν = (Ei − Ef )/h.

Based on these postulates of Bohr, calculation of the energy of an atomic electron

moving in one of the allowed orbits is straight forward. From postulate 1, an electron
of charge −e and mass m moving round a nucleus of charge Ze and mass M in an
orbit of radius r with velocity v, we get

1 Ze2 mv 2
= . (33)
4π0 r2 r
From postulate 2, we get

L = mvr = n~, n = 1, 2, 3, . . . (34)

These two together give us

4π0 ~2 n2 n2
r = = a 0 (35)
me2 Z Z
1 Ze2
v = , (36)
4π0 n~
where, a0 ≈ 5.3nm is known as Bohr radius. The ratio between the speed of electron
in the first Bohr orbit (n = 1) and the speed of light is equal to a dimensionless
constant α, known as fine structure constant:

v1 1 e2 1
α = = = , (37)
c 4π0 ~c 137

1
which actually gives the strength of electromagnetic coupling. Now the kinetic and
potential energy of this electron, using (33), are,

mv 2 1 Ze2
K = =
2 4π0 2r
Z ∞
Ze2 1 Ze2
V = − dr = − .
r 4π0 r2 4π0 r
Therefore, the total energy of the electron, E = K + V , moving in an orbit specified
by n of equation (34) is,

mZ 2 e4 1 RZ
E = − 2 2 2
= − 2 , n = 1, 2, 3, . . . (38)
(4π0 ) 2~ n n
i.e. the quantization of orbital angular momentum leads to quantization of orbital
energy. R = 13.6eV is called Rydberg constant. From postulate 3, the frequency of
electromagnetic radiation emitted when the electron makes transition from quantum
state (Ei , ni ) to the quantum state (Ef , nf ) is given by,
2 !
mZ 2 e4

Ei − Ef 1 1 1
ν = = − 2 . (39)
h 4π0 4π~3 n2f ni

The above expression (39) explains the discrete atomic spectral lines i.e. discrete fre-
quency of electromagnetic radiation when electron jumps around among the discrete
energy levels of the atom.
Direct confirmation that the energy states of an atom are quantized came from
the experiment of Frank and Hertz (1914). The experiment provided not only
the evidence of discrete energy states of Hg atom but actually measured the energy
differences between its quantum states.

Wilson-Sommerfeld quantization rules

To interpret two rather successful quantization rules – Planck’s quantization of en-
ergy (10),  = nhν and Bohr’s quantization of angular momentum (34), L = n~
of an electron moving in a circular orbit – in a consistent way, Wilson and Sommer-
feld (1916) offered a scheme that included both Planck and Bohr quantization rules
as special cases. Wilson-Somerfeld quantization rule states that – for any phys-
ical system in which the coordinates are periodic functions of time, the
quantum condition for each coordinate is
I
pq dq = nq h (40)

where q is one of the coordinates, pq is the momentum associated with that coordinate,
nq is a quantum number which takes on integral values and integration is taken over
one period of the coordinate q. For instance, (q, pq ) for one dimensional simple
harmonic oscillator is (x, px ), displacement from center and linear momentum, for
electron moving in an orbit it is angle and orbital angular momentum (θ, Lθ ). Most

2
 H
of the time, equation (40) is refered as quantization of action variable, J = pq dq =
nq h, where J is the action.
The rule for quantization of cavity radiation by Planck (10) can be derived from
action quantization (40). Considering an one-dimensional simple harmonic oscillator
(a whole lot of whichH made up the cavity radiation), the task is to calculate the
quantization integral px dx, where the instantaneous position x and momentum px
are related by the total energy E,

p2x kx2 p2x x2

E = + ⇒ + = 1. (41)
2m 2 2mE 2E/k

A plot in two-dimensional space having having coordinates x and px , called phase

space, the motion of simple harmonic oscillator traces out an ellipse, x2 /a2 +p2x /b2 = 1,
semi-axes being
√
r
2E
a = and b = 2mE. (42)
k
H
The value of px dx is just equal to the area enclosed by the above ellipse, thus
I r
2E 2πE
px dx = π a b = π 2mEi = p . (43)
k k/m

Since,
p for an linear oscillator, the frequency of oscillation is related to k and m
as k/m = 2πν, Wilson - Sommerfeld quantization rule (40) leads to Planck’s
quantization (10), I
E
px dx = = nx h ⇒ E = nx hν. (44)
ν
That is, the only allowed states of oscillation Hare those represented in the phase
space by a series of ellipse with quantized area px dx = nh. The area between two
successive ellipses, i.e. states of oscillation, is equal to h. Hence, Planck’s energy
quantization is equivalent to the quantization of action.
Similarly, Bohr’s quantization of orbital angular momentum follows from action
quantization. For an electron moving in a circular orbit, the appropriate coordinate
is the angle θ, which is a periodic function of time, and corresponding momentum is
orbital angular momentum L, which is a constant (angular momentum is conserved
for inverse-square laws). From (40) it follows that,
I I
pθ dθ = nθ h ⇒ L dθ = nh. (45)

H R 2π
Since L is constant, we have Ldθ = L 0
dθ = 2πL and thus

2πL = nh ⇒ L = n~ (46)

which is Bohr’s quantization condition. A more physical interpretation of the Bohr’s

orbital angular momentum quantization comes from de Broglie’s hypothesis of wave-
particle duality.

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 Motivation for action discretization – classical adiabatic invariants
Pendulum with variable string length: Consider an ideal pendulum consisting of a massless
string of length l with a mass m attached and undergoing simple harmonic motion of small
amplitude A i.e. small angle θ. The equaiton of motion of the pendulum, for small θ, is

d2 x d2 θ g
mg sin θ = −F = −m ⇒ = − θ. (47)
dt2 dt 2 l
The solution of the above differential equation is
r
1 g
θ = A cos(2πνt + α), where ν = . (48)
2π l
The force acting on the mass m when the pendulum makes an instanteneous angle θ is,

mv 2 θ2
 
F = mg cos θ + ≈ mg 1 − + mlθ̇2 (49)
l 2
A2
 
= mg 1 − cos2 (2πνt + α) + mlA2 (2πν)2 sin2 (2πνt + α) (50)
2
Clearly, the force F is time-dependent and maximum when θ = 0. Let us calculate the
average force hF i over one complete time period of motion,
Z T
1
hF i = F dt
T 0
Z T
mgA2 T mlA2 4π 2 ν 2 T
Z Z
1 2
= mg dt − cos (2πνt + α) dt + sin2 (2πνt + α) dt
T 0 2T 0 T 0
1 2
= mg + mgA . (51)
4
The kinetic energy of the pendulum is,
1 1 1
KE = mv 2 = ml2 θ̇2 = ml2 A2 4π 2 ν 2 sin2 (2πνt + α). (52)
2 2 2
Therefore the total energy of the pendulum, using (48) is,
1 1
E = KEmax = mlA2 × 4π 2 ν 2 l = mgA2 l. (53)
2 2
H
The action J = pθ dθ being,
I Z T
2 2 2 2 2 T E
J = ml θ̇dθ = ml A 4π ν sin2 (2πνt + α) dt = ml2 A2 4π 2 ν 2 = , (54)
0 2 ν
which is a constant.
Next consider an external agency to shorten length of the string slowly by pulling it
smoothly – the string is shorten by ∆l over a time spanning many periods such that change
of length over one period δl satisfies δl/l  1. Such a slow change in a parameter of
the system is termed as adiabatic while the system itself is undergoing harmonic motion
throughout the time. Work done by external agency over one period is
1
δW = hF i δl = mg δl + mgA2 δl (55)
4

4
where the first term is work done against gravity and second term is the increase in kinetic
energy δE as the mass goes up. Energy of the pendulum for fixed length is Emax = mgA2 l/2,
therefore,
δE 1 δl
= . (56)
E 2 l
Shortening the length l by δl results in increase of frequency δν,
 r 
1 g 1 δl |δν| 1 δl
δν = δ = − ν ⇒ = (57)
2π l 2 l ν 2 l

Putting the above two equations (56, 57) together we obtain,

δE δν
=
E ν
which upon integration yield adiabatic invariant (an adiabatic invariant is a property of a
physical system which stays constant when changes are made slowly)

E
≈ constant. (58)
ν

The action for the system, where the angular momentum is given by pθ = ml2 θ̇, is
I
E
pθ dθ = (59)
ν
The motion of the pendulum when its length changes slowly over time is not quite periodic
over each cycle. However, the classical action remains approximately constant as long the
change is very slow ⇒ the classical action is an adiabatic invariant. Wilson and Sommer-
feld formulated action quantization by equating the quantum number of a system with its
classical adiabatic invariant.