Introduction to Quantum Physics

The era of bold ideas

1. Blackbody radiation and Planck’s hypothesis

An object at any temperature emits thermal radiation.

Figure 40.2 and 40.4 left photo

A black body is an ideal system that absorbs all radiation incident on it. A good approximation of a black
body is a hold leading to the inside of a hollow object.

Figure 40.1

The nature of the radiation emitted from a black body depends only on the temperature of the cavity walls
(and independent of the materials, shape or volume).

Once the phenomenon is known, one need to quantity the amount and set up relevant equation (laws) to
describe it. So the amount of thermal radiation was measured according to different wavelength and
compared to model calculations.

Figure 40.3

1a. Wein’s displacement laws

This law describes the wavelength that the radiation intensity is the greatest when the black body is at
temperature T.

maxT = 2.898  103 m-K.

Stefan’ Law
The second law describes that the total power of radiation emitted increases with temperature.

P = AeT4.

 (= 5.6696  108 W/m2-K4) is called the Stefan’s constant. A is the area of the blackbody (the hole). For
black body, emissivity e = 1. So if we talk about the intensity I, which is defined as P/A,

I = T4 (for black body only)

Rayleigh-Jeans Law predicts

I(,T) = 2ckBT/4.

The model assumes that the cavity walls are treated as a set of oscillators that emit electromagnetic waves
at all wavelength. This model leads to an average energy per oscillator that is proportional to T. Rayleigh-
Jeans Law correctly explains the intensity of blackbody radiation at the long wavelength end of the
spectrum.

Figure 40.4

Rayleigh-Jeans Law cannot explain the intensity at the short wavelength end of the spectrum. Also, it
predicts the total intensity to be infinity. This is in strong disagreement with experiment and contradicts
common sense.

In 1900, Planck was able to guess the correct formula and come up with a “strange” explanation.
 I(,T) = 2hc/[5exp(hc/kBT  1)].

The formula fit the data over the whole spectrum, and over all temperatures. The constant h (6.626  1034
J-s) is a fundamental constant called the Planck’s constant.

In this theory, Planck’s two bold and controversial assumptions are:

1. The molecules (oscillators) can have only discrete values of energy En given by

En = nhf. (for the oscillator)

n is a natural number called a quantum number, and f is the natural frequency of the oscillation of the
molecules.

Because the energy of a molecule can have only discrete value given by the above equation, we say the
energy is quantized. Each discrete energy value represents a different quantum state for the molecule,

2. The molecules emit or absorb energy in discrete packets that later came to be called photons. The
molecules emit or absorb these photons by “jumping” from one quantum state to another. Hence the
energy of one photon corresponding to the energy difference between to adjacent quantum states is

E = hf. (for photon)

Quantum Physics begin with the knowledge that energy of molecule and photon are quantized.

2. The Photoelectric Effect

In the latter part of the 19th century, experiments showed that light incident on certain metal surfaces cause
electrons to be emitted from the surfaces. This is known as the photoelectric effect. The emitted electrons
are called photoelectrons.

As usual, detail measurement is done so that one hopes to get a few formulae.

Figure 40.6 and 40.7

Different frequencies of light were used, and also different intensities of light were used in the experiment.
The key questions are: 1. How many photoelectrons are there? 2. How energetic are these photoelectrons?

The amount of photoelectrons can be deduced from the saturated current measured in the experiment when
the potential difference is positive.

The (kinetic) energy of the photoelectrons can be deduced by setting up a negative potential difference to
repel them. The most energetic photoelectron can only by stopped by the highest negative potential
difference. The absolute value of this maximum potential difference is called the stopping potential Vs.

Assuming the usual laws of mechanics hold, the maximum kinetic energy of the photoelectrons are found
to be

Kmax = eVs.

Several features of this simple photoelectric phenomenon cannot be explained by classical physics or the
wave theory of light.

1. No photoelectrons are emitted if the frequency of the incident light falls below some cutoff frequency
fc, which is a characteristic of the materials being illuminated, no matter how one turn up the intensity.
2. The maximum kinetic energy of the photoelectrons is independent of light intensity.
3. The maximum kinetic energy of the photoelectrons increases with increasing light frequency (and also
depends on materials).
4. Photoelectrons are emitted from the surface almost instantaneously (less than 10 9 s after the surface is
illuminated), even at low light intensity.

Try to see the implications yourselves. The key question is how the energy of light is transferred to that of
the photoelectron. Normally one would think if we increase the intensity, more energy will be transmitted
to each photoelectron. But the experimental data shows that the energy of each photoelectron remains
unchanged, but instead, the number of photoelectron is increased. One natural interpretation is that light
energy is carried in from of packets called photon. The energy of each photo depends only on the light
frequency, but not on the intensity. The number of photon is directly proportional to the light intensity.

Figure 40.8

Einstein borrowed some idea from Planck, by taking that the energy of a photon is

E = hf. (for photon)

This energy is transmitted totally to the photoelectrons. Part of this energy is used to overcome the
potential energy of attraction by the metal. All that remained will appear as the kinetic energy of the
photoelectron. The photoelectrons with maximum kinetic energy have “paid” the minimum potential
energy to escape.

The minimum energy that an electron is bound to the metal is called the work function . So the equation
of energy balance for the most energetic photoelectrons is

Kmax = hf   Equation (1)

 eVs = hf  .

Experiments on Vs versus f verify this equation.

Figure 40.9

The key discussion using Einstein’s idea is the followings:

1. That the effect is not observed below a cutoff frequency follows from the fact that the energy of the
photon must be greater than or equal to . If the energy of the incoming photo does not satisfy this
condition, the electrons are never ejected from the surface, regardless of the light intensity.
2. That Kmax is independent of light intensity can be understood by means of the following argument: If
the light intensity is doubled, the number of photon is doubled, which doubles the number of
photoelectrons emitted. However, their maximum kinetic energy, which equals hf  , depends only
on the light frequency and the work function, not on the light intensity.
3. That Kmax increases with increasing frequency is easily understood with Equation (1).
4. That photoelectrons are emitted almost instantaneously is consistent with the particle theory of light, in
which the incident energy arives at the surface in small packets and there is a one-to-one interaction
between photons and photoelectrons. In this interaction the photon’s energy is imparted to an electron
that then has enough energy t leave the metal. This is in contrast to the wave theory, in which the
incident energy is distributed uniformly over a large area of the metal surface.

Sometimes the cutoff wavelength c is used. One can calculated that starting from the cutoff frequency fc.

c = c/fc.

3. The Compton effect

In the photoelectric effect, it is clear that light behaves as particles (photons) when light transmits energy to
an electron in a metal. In 1919 Einstein concluded that photon also carries momentum. Therefore, photon
has most of the characteristics of a particle. The momentum is given by

p = E/c = hf/c. = h/.

The experimental evidence (known as the Compton effect) was presented by Compton and Debye in 1922.
The experiment was on the interaction of x-ray with electrons in matter. The result can in interpreted as the
collision of a x-ray photon by a free electron. The key point is that both energy and momentum has to be
conserved.

Figure 40.10 and 40.11.

In the data, one can that the outgoing x-ray is of two different types. One type is has wavelength o. This
is the same energy as the incident x-ray. The other has a longer wavelength (lower energy) and its energy
depends on the angle of scattering . This is the x-ray photon that has collided with a single electron. The
wavelength of the photon are given by

’  o = (h/mec) (1  cos).

This is called the Compton shifted equation, and the factor h/mec is called the Compton wavelength.

c = h/mec = 0.00243 nm.

Deviation of the Compton Shift Equation

Basically one need to apply the conservation of energy (1 equation) and conservation of linear momentum
(2 equations). Assume electron initially at rest, and neglect the work function of material. Final energy of
electron = Ke = mec2  mec2.

Conservation of energy:

hc/o + 0 = hc/’ + Ke = hc/’ + mec2  mec2. (1)

Conservation of linear momentum:

x-component: h/o + 0 = (h/’)cos. + mev cos. (2)

y-component: 0 + 0 = (h/’)sin.  mev sin. (3)

So we have three equations and the unknowns are ’, , and v (). We want to find ’, so we need to
eliminate , and v.

Use equation (2) and (3) to eliminate  (the cosine formula in mathematics):

(mev)2 = (h/o)2 + (h/’)2  2(h/o)(h/’) cos. (4)

The rewrite equation (1) to find .

mec2 = hc/o  hc/’ + mec2

 mec = h/o  h/’ + mec (5)

Then use (1) to eliminate both  and v. This can be done by taking the square of (5) and then subtract (4).
 (mec)2  (mev)2 = (h/o  h/’ + mec)2  (h/o)2  (h/’)2 + 2(h/o)(h/’) cos

 2me2 (c2  v2) = 2h2/o’ + me2c2 + 2mec(h/o  h/’) + 2h2/o’ cos

 me2c2 = 2h2/o’ + me2c2 + 2mec(h/o  h/’) + 2h2/o’ cos

 0 = 2h2/o’ + 2mech(’  o)/o’ + 2h2/o’ cos

 0 = h + mec(’  o) + h cos

 mec(’  o) = h  h cos

 ’  o = h/mec (1  cos).

4. Atomic Spectra
All objects emit thermal radiation characterized by a continuous distribution, but not all objects are black
body and most often object are not be in thermal equilibrium.

Low-pressure gases subjected to an electric discharge emit discrete line spectrum. This is called an
emission spectrum. Observation and analysis of this emitted light is called emission spectroscopy.

Figure 40.13

An absorption spectrum is obtained by passing light from a continuous source through a gas or a dilute
solution of the element being analysis.
Most bright lines that occur on the emission spectrum occur as dark lines on the absorption spectrum. In
general, not all line appears on the emission spectrum.

Spectroscopy has been the principal means in analyzing stars and also galactic matters. Spectroscopy also
found many applications in atmospheric science and in the laboratory in analyzing matters.

From 1860 to 1885, scientists accumulated a great deal of data on atomic emission using spectroscopic
measurements. The theoretical breakthrough in this area came in 1885 when a Swiss school teacher, J.J.
Balmer, found an empirical formula to the four visible emission lines of hydrogen.

Figure 40.14

The complete set of lines is called the Balmer series. Balmer’s formula is

1/ = RH(1/22 – 1/n2), n = 3, 4, 5, 6, …..

RH (= 1.0973732  107 m–1) is called the Rydberg constant.

Although Balmer’s formula looks simple, it is actually very difficult to guess. But once the formula is
known, other series were easier to guess.

The Lyman series: 1/ = RH(1/12 – 1/n2), n = 2, 3, 4, 5, …..

The Paschen series: 1/ = RH(1/32 – 1/n2), n = 4, 5, 6, 7, …..

The Brackett series: 1/ = RH(1/42 – 1/n2), n = 5, 6, 7, 8, …..

All of these formulae were empirical. That means no theoretical basis existed for them. The next
challenge is to work out what fundamental laws govern these formulae.
5. Bohr’s Quantum Model of the Atom

1. Electrostatic force governed by Coulomb’s law. Other forces are unimportant. Electron undergoes
circular orbit governed by Newton’s law.
2. Only certain orbits are allowed. Electrons in these orbits do not emit electromagnetic radiation
according to the classical laws of electromagnetism (Maxwell’s equation).
3. New laws of EM radiation: Radiation is emitted when electron jumps from one orbit to another orbit
(one state to another state, one energy level to another energy level).

Ei  Ef = hf.

4. New equation governing the allowed orbits. Allowable orbits are those satisfying the following:

mevr = n(h/2), n = 1, 2, 3, 4, …... (1)

Using these assumptions, one can start getting predictions from the model. The main ingredient is
Newton’s law and that will be used to calculate the radius of the circular orbit.

kee2/r2 = mev2/r

 kee2/r = mev2. (2)

The key objective is to get the energy of electron in these allowable orbits.

E = K + U = mev2/2  kee2/r =  kee2/2r. (3)

What are the unknowns in equation (3)? v and r are unknowns. In (3) we have already eliminated v using
(2). Furthermore, we need to eliminate r. Take the square of (1) and then divide that by (2),

rn = n2h2/meke2 = n2ro. (4)

The smallest radius (happens at n = 1) is called the Bohr radius ro.

ro = h2/meke2 = 0.0529 nm = 0.529 Angstrom.

Putting (4) into (3), we finally get the energy of the allowable orbits.

En =  kee2/2r =  (kee2/2ro) (1/n2) =  13.606/n2 eV. (5)

Only energies satisfying this equation (called energy levels) are permitted. The lowest allowed energy
level is called the ground state. Its value is E1 = –13.606 eV. The next energy level, the first excited state,
has n = 2 and energy E2 = E1/22 = –3.401 eV. The following figures show the relations.

The uppermost level, corresponding to n = . It has r =  and E = 0, represents the state for which the
electron is removed from the atom. The minimum energy required to remove one electron from the atom
(in the ground state) is called the ionization energy. Bohr’s calculation predicts that the ionization energy
is 13.606 eV. This is known to agree with experiment at that time.

The frequency of the photon emitted when the electron jump from an outer orbit to an inner orbit is
calculated from the 3rd assumption (that is Ei  Ef = hf).

1/ = f/c = (Ei – Ef)/hc = (kee2/2rohc) (1/nf2  1/ni2).

Compare to the empirical equation obtained from experiment, 1/ = Rh(1/nf2  1/ni2), there is a direct
prediction of the Rydbery constant.

RH = kee2/2rohc = 1.0973732  107 m–1.

The agreement between the predicted value and the experimental value is within 1%. In this way, all the
spectral lines of the hydrogen emission spectrum are explained to within a good accuracy. Bohr’s work
was soon recognized as very important. This is the birth of the “old” quantum mechanics.

What is the weakness of the Bohr model?

1. It works well only for atoms (ions) with 1 electron. It does not work for more complicated atoms or
molecules.
2. The fourth assumption is not well-understood (mevr = n(h/2), n = 1, 2, 3, 4, ……).

Bohr’s Correspondence Principle

Quantum Physics is in agreement with classical physics where the difference between quantized levels
becomes vanishingly small.

6. Photons and electromagnetic waves

We use both the wave model and particle model and admit that the true nature of light is not describable in
terms of any single classical picture.

The particle model and the wave model complement each other.

Wave-particle duality: Light has a dual nature. It exhibits both wave and particle characteristics.

7. The wave nature of particles

Because Photons have both wave and particle characteristics, perhaps all form of matter have both
properties.

Once the right concept is introduced, the next to guess the possible relations and test them experimental.
So we need a relation (equation) that tell us the frequency and wavelength of matter/particle wave”.

The relation is borrowed from that of photon.

 = h/p = h/mv,

f = E/h.

The first relation (de Broglie relation) is the key breakthrough. The wavelength is called the de Broglie
wavelength of a particle. It was proposed by de Broglie in 1923, and it was soon verified by experiment on
electron diffraction, to be discussed in the next section.

The Davisson-Germer Experiment

Wave properties can be demonstrated and wavelength measurement can be measured by interference
experiment. The key demonstration of matter wave is on the diffraction of electron wave by crystals.

Three years after de Broglie propose the de Broglie relation for matter wave, Davisson and Germer saw the
diffraction pattern of low-energy electron by nickel crystal. The large nickel crystal acts as diffraction
grating that allows the wavelength of the electron wave to be determined. Their result confirms the de
Broglie relation.

The problem of understanding the dual nature of matter and radiation is conceptually difficult because the
two models seem to contradict each other. This problem as it applies to light was discussed earlier. Bohr
helped to resolve this problem in his principle of complementarity, which states that the wave and particle
models of either matter or radiation complement each other.