7.

1 ENERGY QUANTIZATION 251

The overthrow of classical mechanics and its replacement by quantum mechanics was Maximum
driven, as always in science, by noticing that experimental observations conflicted of ρ
with the predictions of accepted theory. Here we outline three examples of experi-
ment overthrowing current theory, which came to light at the end of the nineteenth

Energy distribution, ρ
century and which drove scientists to the view that energy can be transferred only in Increasing
discrete amounts. temperature

(a) Black-body radiation

A hot object emits electromagnetic radiation. At high temperatures, an appreciable
proportion of the radiation is in the visible region of the spectrum, and a higher
proportion of short-wavelength blue light is generated as the temperature is raised.
This behaviour is seen when a heated metal bar glowing red hot becomes white hot
when heated further. The dependence is illustrated in Fig. 7.3, which shows how the
energy output varies with wavelength at several temperatures. The curves are those Wavelength, λ
of an ideal emitter called a black body, which is an object capable of emitting and
absorbing all wavelengths of radiation uniformly. A good approximation to a black Fig. 7.3The energy distribution in a black-
body is a pinhole in an empty container maintained at a constant temperature, body cavity at several temperatures. Note
because any radiation leaking out of the hole has been absorbed and re-emitted inside how the energy density increases in the
so many times as it reflected around inside the container that it has come to thermal region of shorter wavelengths as the
equilibrium with the walls (Fig. 7.4). temperature is raised, and how the peak
shifts to shorter wavelengths. The total
The approach adopted by nineteenth-century scientists to explain black-body radi-
energy density (the area under the curve)
ation was to calculate the energy density, dE, the total energy in a region of the elec- increases as the temperature is increased
tromagnetic field divided by the volume of the region (units: joules per metre-cubed, (as T 4).
J m−3), due to all the oscillators corresponding to wavelengths between λ and λ + dλ.
This energy density is proportional to the width, dλ, of this range, and is written
dE(λ,T ) = ρ(λ,T )dλ (7.3)
Detected
where ρ (rho), the constant of proportionality between dE and dλ, is called the den-
radiation
sity of states (units: joules per metre4, J m−4). A high density of states at the wavelength
λ and temperature T simply means that there is a lot of energy associated with wave-
lengths lying between λ and λ + dλ at that temperature. The total energy density in a
Pinhole
region is the integral over all wavelengths:
∞
E(T ) = ! 0
ρ(λ,T)dλ (7.4)
Container
at a
temperature T
and depends on the temperature: the higher the temperature, the greater the energy
density. Just as the mass of an object is its mass density multiplied by its volume, the total Fig. 7.4An experimental representation
energy within a region of volume V is this energy density multiplied by the volume: of a black body is a pinhole in an otherwise
closed container. The radiation is reflected
E(T) = VE(T) (7.5) many times within the container and
comes to thermal equilibrium with the
The physicist Lord Rayleigh thought of the electromagnetic field as a collection of
walls at a temperature T. Radiation leaking
oscillators of all possible frequencies. He regarded the presence of radiation of fre- out through the pinhole is characteristic of
quency ν (and therefore of wavelength λ = c/ν) as signifying that the electromagnetic the radiation within the container.
oscillator of that frequency had been excited (Fig. 7.5). Rayleigh knew that according
to the classical equipartition principle (Fundamentals F.5b), the average energy of
each oscillator, regardless of its frequency, is kT. On that basis, with minor help from
James Jeans, he arrived at the Rayleigh–Jeans law for the density of states:

8πkT Rayleigh–Jeans
ρ(λ,T) = law
(7.6)
λ4
where k is Boltzmann’s constant (k = 1.381 × 10−23 J K−1).
252 7 QUANTUM THEORY: INTRODUCTION AND PRINCIPLES
(a)
(b)
Fig. 7.5 The electromagnetic vacuum can be
regarded as able to support oscillations of
the electromagnetic field. When a high
frequency, short wavelength oscillator
(a) is excited, that frequency of radiation is
present. The presence of low frequency,
long wavelength radiation (b) signifies
that an oscillator of the corresponding
frequency has been excited.
Rayleigh–Jeans
law
Energy distribution, ρ
Experimental
Wavelength, λ
Fig. 7.6The Rayleigh–Jeans law (eqn 7.6)
predicts an infinite energy density at short
wavelengths. This approach to infinity is
called the ultraviolet catastrophe.
A brief comment
The series expansion of an exponential
function is e x = 1 + x + 12 x 2 + · · · . If x << 1,
a good approximation is e x ≈ 1 + x. For
example, e0.01 = 1.010 050 . . . ≈ 1 + 0.01.
Although the Rayleigh–Jeans law is quite successful at long wavelengths (low fre-
quencies), it fails badly at short wavelengths (high frequencies). Thus, as λ decreases,
ρ increases without going through a maximum (Fig. 7.6). The equation therefore pre-
dicts that oscillators of very short wavelength (corresponding to ultraviolet radiation,
X-rays, and even γ-rays) are strongly excited even at room temperature. The total
energy density in a region, the integral in eqn 7.4, is also predicted to be infinite at
all temperatures above zero. This absurd result, which implies that a large amount of
energy is radiated in the high-frequency region of the electromagnetic spectrum, is
called the ultraviolet catastrophe. According to classical physics, even cool objects
should radiate in the visible and ultraviolet regions, so objects should glow in the dark;
there should in fact be no darkness.
In 1900, the German physicist Max Planck found that he could account for the
experimental observations by proposing that the energy of each electromagnetic
oscillator is limited to discrete values and cannot be varied arbitrarily. This proposal
is contrary to the viewpoint of classical physics in which all possible energies are
allowed and every oscillator has a mean energy kT. The limitation of energies to
discrete values is called the quantization of energy. In particular, Planck found that
he could account for the observed distribution of energy if he supposed that the per-
mitted energies of an electromagnetic oscillator of frequency ν are integer multiples
of hν :
E = nhν n = 0, 1, 2, . . . (7.7)
where h is a fundamental constant now known as Planck’s constant. On the basis of
this assumption, Planck was able to derive the Planck distribution:
8πhc
ρ(λ,T) = hc/λkT
Planck distribution (7.8)
λ (e 5
− 1)
This expression fits the experimental curve very well at all wavelengths (Fig. 7.7), and
the value of h, which is an undetermined parameter in the theory, may be obtained
by varying its value until a best fit is obtained. The currently accepted value for h is
6.626 × 10−34 J s.
As usual, it is a good idea to ‘read’ the content of an equation:
1. The Planck distribution resembles the Rayleigh–Jeans law (eqn 7.6) apart from
the all-important exponential factor in the denominator. For short wavelengths,
hc/νkT >> 1 and ehc/λkT → ∞ faster than λ5 → 0; therefore ρ → 0 as λ → 0 or ν → ∞.
Hence, the energy density approaches zero at high frequencies, in agreement with
observation.
2. For long wavelengths, hc/λ kT << 1, and the denominator in the Planck distribu-
tion can be replaced by
A hc D hc
ehc/λkT − 1 = B 1 + + · · ·E − 1 ≈
C λ kT F λ kT
When this approximation is substituted into eqn 7.8, we find that the Planck dis-
tribution reduces to the Rayleigh–Jeans law.
3. As we should infer from the graph in Fig. 7.7, the total energy density (the integ-
ral in eqn 7.4 and therefore the area under the curve) is no longer infinite, and in fact
∞
E(T) = ! 0
λ (e5
8πhc
hc/λkT
− 1)
dλ = aT 4 with a=
8π5k4
15(hc)3
(7.9)
That is, the energy density increases as the fourth power of the temperature.
 7.1 ENERGY QUANTIZATION 253

• A brief illustration

We can now see why an incandescent lamp is so effective. Before it is switched on, the
energy density inside the glass envelope corresponds to about 20°C (293 K). When it is
switched on, the temperature of the filament rises to about 2000 K. The energy density
increases by a factor of (2000 K/293 K)4 ≈ 2000, and it generates nearly white light. •

ρ /{8π(kT)5/(hc)4}
It is easy to see why Planck’s approach was successful while Rayleigh’s was not. The
thermal motion of the atoms in the walls of the black body excites the oscillators of the
electromagnetic field. According to classical mechanics, all the oscillators of the field
share equally in the energy supplied by the walls, so even the highest frequencies are
excited. The excitation of very high frequency oscillators results in the ultraviolet
Nice catastrophe. According to Planck’s hypothesis, however, oscillators are excited only
explanation if they can acquire an energy of at least hν. This energy is too large for the walls to sup-
ply in the case of the very high frequency oscillators, so the latter remain unexcited. 0 0.5 1 1.5 2
λ
λkT/hc
The effect of quantization is to reduce the contribution from the high frequency
oscillators, for they cannot be significantly excited with the energy available.
Fig. 7.7The Planck distribution (eqn 7.8)
accounts very well for the experimentally
(b) Heat capacities
determined distribution of black-body
In the early nineteenth century, the French scientists Pierre-Louis Dulong and Alexis- radiation. Planck’s quantization hypothesis
Thérèse Petit determined the heat capacities, CV = (∂U/∂T)V (Section 2.4), of a num- essentially quenches the contributions of
ber of monatomic solids. On the basis of some somewhat slender experimental high frequency, short wavelength
evidence, they proposed that the molar heat capacities of all monatomic solids are the oscillators. The distribution coincides with
the Rayleigh–Jeans distribution at long
same and (in modern units) close to 25 J K−1 mol−1.
wavelengths.
Dulong and Petit’s law is easy to justify in terms of classical physics in much the
interActivity Plot the Planck
same way as Rayleigh attempted to explain black-body radiation. If classical physics
distribution at several temperatures
were valid, the equipartition principle could be used to infer that the mean energy of and confirm that eqn 7.8 predicts the
an atom as it oscillates about its mean position in a solid is kT for each direction of dis- behaviour summarized by Fig. 7.3.
placement. As each atom can oscillate in three dimensions, the average energy of each
atom is 3kT; for N atoms the total energy is 3NkT. The contribution of this motion to
the molar internal energy is therefore
Um = 3NAkT = 3RT (7.10a)
because NAk = R, the gas constant. The molar constant volume heat capacity is then
predicted to be

A ∂U D
CV,m = B m E = 3R (7.10b)
C ∂T F V

This result, with 3R = 24.9 J K−1 mol−1, is in striking accord with Dulong and Petit’s
value.
Unfortunately, significant deviations from their law were observed when advances
in refrigeration techniques made it possible to measure heat capacities at low temper-
atures. It was found that the molar heat capacities of all monatomic solids are lower
than 3R at low temperatures, and that the values approach zero as T → 0. To account
for these observations, Einstein (in 1905) assumed that each atom oscillated about its
equilibrium position with a single frequency ν. He then invoked Planck’s hypothesis
to assert that the energy of oscillation is confined to discrete values, and specifically to
nhν, where n is an integer. Einstein discarded the equipartition result, calculated the
vibrational contribution of the atoms to the total molar internal energy of the solid
(by a method described in Section 16.4), and obtained the expression known as the
Einstein formula: