BAB 3

Mekanika Kuantum

By the end of the nineteenth century three types of observations made it apparent that
classical mechanics could not give correct results when it was appiied to molecular and atomic
phenomena. These observations involved studies of atomic spectra, blackbody radiation, and the.
photoelectric effect. In the section that follows, each of these experiments is discussed, and it is
shown how the basic assumptions of classical mechanics had to be abandoned. Following this,
quantum mechanics is introduced by a series of postulates and these postulates are then applied to
calculations on some simple systems.

3-1 ATOMIC SPECTRA, BLACKBODY RADIATION, AND THE PHOTOELECTRIC

EFFECT

The discipline of spectroscopy began in the early part of the nineteenth century with the
observation of the sunlight spectrum by Josef F raunhofer. The study of the spectra of atoms was
begun in l86l by Kirchoff and by Bunsen, who extensively studied the spectrum of the alkali
metals. In 1885, Balmer discovered the series of lines in the spectrum of atomic hydrogen that now
bears his name, and found that he could write an empirical relationship that gave the positions of
all the lines This relationship was

Ada Persamaan (3-1)

where λ is the wavelength of the observed line and R is a constant called the Rydberg
constant. This constant is one or the most accurately known physical constants and has the value
l09,677.581 cm-1.

EXERCISE 3-1 Equation 3-l predicts the qualitative features of the spectra of other atoms besides
hydrogen, especially the spectra of the alkali metals. In the latter case the constant R is replaced
by other constants. Calculate the position of the lines in the hydrogen atom in units of R for n, 3,
4, 5, 10, 100, ∞. Plot these results along a horizontal scale in l/λ. Note how the lines converge to a
limiting value. This limiting value is called the series limit.

There were several striking features about atomic spectra. The first was the sharpness of
the spectral lines. Apparently, energy was not emitted or absorbed by atoms in bands, or in a
continuous fashion, but only at certain very precise frequencies. It was this sharpness of spectral
lines that enabled the constant R to be determined with such accuracy. The second striking feature
was the fact that the spectrum of each kind of atom was highly characteristic. In fact, the best proof
for the presence of a particular element in a sample was the existence of its characteristic spectrum.
It is clear that any theory of the structure of atoms would have to explain these two features of
atomic spectra. In addition. for the hydrogen atom, the characteristic frequencies would have to be
those predicted by Eq. 3-1. We see later how classical mechanics was at a loss to account for these
facts if the Rutherford model of the atom were accepted.

Although the spectroscopic results had been accumulating for some time, the experiments
that hrst led to questions about the validity of classical mechanics were those designed to measure
the frequency (or wavelength, since the two are related by frequency xwavelengthaspeed of light)
dependence of biackbody radiation. A detailed discussion of blackbody radiation is beyond the
scope of this text, but enough of the basic features can be outlined to acquaint the student with the
experimental results and their significance. ‘

Blackbody radiation is a familiar phenomenon even though the name may seem
mysterious. When the heating element of an electric stove is turned on, it emits radiation. This
radiation can be detected by placing one’s hand at some distance above the heating element. If the
stove is on low heat, the radiation can be detected by feeling only and not by sight. If the heat is
turned up the stove element will begin to glow first red, then white, and, if the temperature could
be raised high enough, even blue. This change in color is evidence that the frequency distribution
of the radiation emitted by the hot body is changing with temperature.

In the laboratory, blackbody radiation is studied by constructing a cavity that is insulated

so that the only energy that can be absorbed is energy added in the form of heat to raise the
temperature of the cavity. The cavity is evacuated, and there is a small hole in one side of the
apparatus through which radiation can pass. The approximation is made that the radiation

Coming from the hole in the cavity is a good sample of the radiation inside the cavity” The
intensity of the radiation emitted from the hole is then studied as a function of wavelength at
several different cavity temperatures. When this is done, data like those plotted in Figure 3-1 are
obtained.

Ada Diagram

Figure 3-1 typical data for the intensity of blackbody radiation plotted as a function of wavelength.
The student should note the falloff of intensity in the ultraviolet region of the spectrum as well as
the “blue shift” of the maximum as the temperature increases. The dashed line is the prediction of
the Rayleigh-jeans formula at 2000oK.

By applying classical statistical mechanics and the properties of wave motion, one can
calculate the number of light waves between frequencies v and v-t-dv in a box of volume V [ l,2
]. This number is
 Ada persamaan ( 3-2 )

To calculate the frequency distribution as a function of temperature, Lord Rayleigh and J.

H.1eans assumed that each electromagnetic wave had its classical value of the energy kT, where k
is the Boltzmann constant. This result comes from the theorem of equipartition of energy in
classical statistical mechanics. A loose statement of the theorem is that there is a contribution of
½ kT to the energy of a system f or each squared term that appears in the expression for the energy
of the microscopic component making up the system. Since the energy of a classical light wave is
proportional to δo2 + Ho2, where δo2 and Ho are the amplitudes of the oscillating electric and
magnetic fields of the light wave respectively, there are two squared terms and the contribution to
the system energy will then be kT. (See [1-3].)

For unit volume. this assumption, and Eq. 3 2, gives the Rayleigh-Jeans formula

Ada Persamaan ( 3-3 )

where p(v, T) dv is the energy density of radiation between frequencies v and v + dv at

absolute temperature T and is proportional to 'the intensity of the light coming from the hole in the
cavity at these frequencies. A plot of Eq. 33 for T= 2000°K is also shown in Figure 3-l. The student
will notice that the {it of Eq. 3 3 is good at long wavelengths (low frequencies) but that the fit gets
worse as the wavelength decreases and becomes qualitatively wrong at short wavelengths in that
the Rayleigh-Jeans formula does not predict the maximum and sharp falloff. (Rayleigh and Jeans
realized that this result was incorrect, but they did not know hoiv to remedy the situation using the
assumptions of classical mechanics.) The inability of classical mechanics to explain the falloff of
radiation density in the ultraviolet region of the spectrum has been dubbed the “ultraviolet
catastrophe.”

Max Planck next attacked this problem. He used the fact, as did Rayleigh and Jeans, that
the radiation on the inside of a heated body arises because of the emission from the vibrating
constituents of the material. Rather than assume that these vibrations could emit energyof
anyvalue. he proposed that energy could only° be emitted in discrete amounts, called quanta.
Planck hypothesized that these fundamental quanta had an energy equivalent to hv,

Where v was the fundamental frequency of the oscillator and where h is the now famous
Planck's constant. At the time. This ad hoc assumption had no precedent and was justified only in
that it gave the right answer. In this assumption, the idea of the existence of discrete energy states
in matter was born.
 Using Planck's hypothesis, the number of light waves between frequencies v and dv is not
that given by Eq. 3-2 but is rather (see, for example, [3])

Ada persamaan ( 3-4)

Which, when combined with the energy of a light wave of this frequency (Irv), gives the Planck
radiation law

Ada persamaan ( 3-5 )

Equation 3-5 is in exact agreement with experiment. (See Exercise 3-3.)

EXERCISE 3-2 Show that in the limit of long wavelength (low frequency), Eq. 3-5 goes over into
Eq. 3-3. Him: Expand the exponential in a McLaurin series and argue about what happens when
Iw becomes less than kT.

EXERCISE 3-3 The function agreeing with experiment in Figure 3-1 is not the function p'(v,T) dv
but rather p’(λ,T) dλ. Using the fact that λv =c, and therefore that dv = -c/λ2dλ ,show that

Ada Persamaan

This function agrees with the experimental results in Figure 3-1.

It was 'not long before Planck’s quantity hv had another application. In 1905, in order to explain
the photoelectric effect, Albert Einstein postulated that light energy also had to be quantized.
Planck originally thought that only the oscillators m a blackbody were quantized.
The photoelectric effect can best be illustrated by the description of an actual experiment. A
schematic diagram of the apparatus is shown in Figure 3-2. The apparatus consists of a special cell
C which contains a screen or grid and a receiving element constructed of a piece of metal which
has been plated with a thin film of the metal to be studied. When the switch in Figure 3-2 is at
position A, the screen is connected to the receiver element through a battery and a sensitive
galvanometer G. The special cell is highly evacuated. Also included is a device R for changing the
potential of the screen with respect to the receiving element. When light strikes the surface