Introduction to Quantum Physics

Many experimental and theoretical problems in physics were resolved by the special theory of
relativity. However, many other problems, neither relativity nor classical physics could provide a
theoretical answer. Attempts to apply the laws of classical physics to explain the behavior of matter
on the atomic scale were not successful. For example, the emission of discrete wavelengths of light
from atoms in a high-temperature gas could not be explained within the framework of classical
physics.
As time progressed, quantum mechanics became a new theory that was successful in explaining
the behavior of particles of microscopic size. Max Planck was the first to use the ideas of quantum
theory to explain a physical phenomenon.

Blackbody Radiation and Planck’s Hypothesis

An object at any temperature emits electromagnetic waves in the form of thermal radiation from
its surface. The characteristics of this radiation depend on the temperature and properties of the
object’s surface. Such a radiation consists of a continuous distribution of wavelengths from all
portions of the electromagnetic spectrum. If the object is at room temperature, the wavelengths of
thermal radiation are mainly in the infrared region and hence the radiation is not detected by the
human eye. As the surface temperature of the object increases, the object eventually begins to glow
visibly red, and at sufficiently high temperatures, the glowing object appears white.

These phenomena could not be explained by the classical

theory of thermal radiation. The basic problem was in
understanding the observed distribution of wavelengths in the
radiation emitted by a black body. A black body is an ideal
system that absorbs all radiation incident on it. The
electromagnetic radiation emitted by the black body is called
blackbody radiation.
A good approximation of a black body is a small hole leading
to the inside of a hollow object as shown Figure 1. Any
radiation incident on the hole from outside the cavity enters
the hole and is reflected a number of times on the interior
Fig. 1: A Physical Model of a Black Body walls of the cavity; hence, the hole acts as a perfect absorber.
The nature of the radiation leaving the cavity through the hole depends only on the temperature of
the cavity walls and not on the material of which the walls are made. The spaces between lumps
of hot charcoal emit light that is very much like blackbody radiation.
The wavelength distribution of radiation from cavities was studied experimentally, and the
following two findings were seen as especially significant:
1. The total power of the emitted radiation increases with temperature, which is the Stefan’s law:
𝑃 = 𝜎𝐴𝑒𝑇 4 (1)
where P is the power in watts radiated at all wavelengths from the surface of an object, 𝜎 = 5.6 ×
𝑊
10−8 𝑚2 𝐾 4 is the Stefan–Boltzmann constant, A is the surface area of the object in square meters,

e is the emissivity of the surface, and T is the surface temperature in kelvins. For a black body, the
emissivity is 𝑒 = 1 exactly.
2. The peak of the wavelength distribution shifts to shorter wavelengths as the temperature
increases. This behavior is described by the following relationship, called Wien’s
displacement law:
𝜆𝑚𝑎𝑥 𝑇 = 2.898 × 10−3 𝑚𝐾 (2)
where 𝜆𝑚𝑎𝑥 is the wavelength at which the curve peaks and T is the absolute temperature of the
surface of the object emitting the radiation. The wavelength at the curve’s peak is inversely
proportional to the absolute temperature; that is, as the temperature increases, the peak is
“displaced” to shorter wavelengths.
To describe the distribution of energy from a black body, we define 𝐼(𝜆, 𝑇)𝑑𝜆 to be the intensity,
or power per unit area, emitted in the wavelength interval 𝑑𝜆. The result of a calculation based on
a classical theory of blackbody radiation known as the Rayleigh–Jeans law is
2𝜋𝑐𝑘𝐵 𝑇
𝐼(𝜆, 𝑇) = (3)
𝜆4
where 𝑘𝐵 is Boltzmann’s constant.
In the classical theory used to derive Eq. (3), the average energy for each wavelength of the
standing-wave modes is assumed to be proportional to 𝑘𝐵 𝑇, based on the theorem of equipartition
of energy.
As 𝜆 approaches zero, the function 𝐼(𝜆, 𝑇) approaches infinity. Hence, according to classical
theory, not only should short wavelengths predominate in a blackbody spectrum, but also the
energy emitted by any black body should become infinite in the limit of zero wavelength. In
 contrast to this prediction, a plot of the experimental data shows that as 𝜆 approaches zero, 𝐼(𝜆, 𝑇)
also approaches zero. This mismatch of theory and experiment was so disconcerting that scientists
called it the ultraviolet catastrophe. (This “catastrophe” – infinite energy occurs as the wavelength
approaches zero; the word ultraviolet was applied because ultraviolet wavelengths are short.)
In the development of a theory of blackbody radiation by Max Planck that leads to an equation for
𝐼(𝜆, 𝑇), Plank made the following assumptions:
1. The cavity radiation came from atomic oscillators in the cavity walls
2. (a) The energy of an oscillator can have only certain discrete values 𝐸𝑛
𝐸𝑛 = 𝑛ℎ𝑣 (4)
where n is a positive integer called a quantum number, 𝑣 is the oscillator’s frequency, and h is
a parameter called Planck’s constant. Because the energy of each oscillator can have only discrete
values given by Eq. (4), we say the energy is quantized. Each discrete energy value corresponds
to a different quantum state, represented by the quantum number n. When the oscillator is in the
𝑛 = 1 quantum state, its energy is ℎ𝑣; when it is in the 𝑛 = 2 quantum state, its energy is 2ℎ𝑣;
and so on.
(b) The oscillators emit or absorb energy when making a transition from one quantum state to
another. The entire energy difference between the initial and final states in the transition is emitted
or absorbed as a single quantum of radiation. If the transition is from one state to a lower adjacent
state - say, from the 𝑛 = 3 state to the 𝑛 = 2 state, Eq. (4) shows that the amount of energy emitted
by the oscillator and carried by the quantum of radiation is
𝐸 = ℎ𝑣 (5)
According to property 2(b), an oscillator emits or absorbs
energy only when it changes quantum states. If it remains
in one quantum state, no energy is absorbed or emitted.
Figure 2 is an energy-level diagram showing the
quantized energy levels and allowed transitions proposed
by Planck. The vertical axis is linear in energy, and the
allowed energy levels are represented as horizontal lines.
The quantized system can have only the energies
represented by the horizontal lines.
Figure 2: Allowed energy levels for
an oscillator with frequency f.
Example 1: Find the peak wavelength of the blackbody radiation emitted by the human body when
the skin temperature is 35°C. Use 𝜆𝑚𝑎𝑥 𝑇 = 2.898 × 10−3 𝑚𝐾
Example 2: Supposed a block is attached to a massless spring causing it to oscillate at a frequency
of 0.563 Hz. Assuming the quantized energy of the oscillator is 2.00 J, find the quantum number
n for the system oscillating with this frequency. Use 𝐸𝑛 = 𝑛ℎ𝑣

The Photoelectric Effect

Experiments showed that when light is incident on certain metallic surfaces, it causes electrons to
be emitted from those surfaces. This phenomenon is known as the photoelectric effect, and the
emitted electrons are called photoelectrons. For an electron to be emitted from a surface, it must
absorb enough energy from the incident radiation to overcome the attraction of the positive ions
in the material of the surface. This attraction causes a potential-energy barrier that normally
confines the electrons inside the materials.
Einstein made the radical proposal that light consisted of particles called photons and each photon
carries energy as given by Eq. (5) and the linear momentum given by
ℎ
𝑝= (6)
𝜆
Using the relation 𝑐 = 𝜈𝜆 where c is the speed of light in vacuum, we can rewrite the momentum
of a photon as:
ℎ ℎ ℎ 𝐸
𝑝= = = = (7)
𝜆 𝑐/𝑣 𝑐 ( ℎ ) 𝑐
𝐸
Several features associated with the photoelectric effect that could not be explained were accounted
for by this proposal. According to Einstein, the maximum energy of the emitted electrons is found
to be:
𝑞𝑉0 = 𝐸𝑚𝑎𝑥
where q is the charge of the electron and 𝑉0 is the stopping potential. Experiment shows that:
1. When light strikes a metal surface, a current flows instantaneously, even for very weak
light.
2. At a fixed frequency, the strength of the current is directly proportional to the intensity of
the light.
3. The stopping potential 𝑉0, and therefore the maximum energy of the emitted electrons,
depends only on the frequency of the light and the type of metal used.
 4. Each metal has a characteristic threshold frequency 𝑣0 such that:
𝑞𝑉0 = ℎ(𝑣 − 𝑣0 )
5. The constant h is found to be the same for all metals, and not surprisingly turns out to be
the same constant used by Planck in his blackbody derivation.
7
Each of these experimental ideas can be explained by accepting that light is made up of particles.
For example, consider observation 2, which is easy to explain in the photon picture. If the intensity
of the light beam is increased, then the number of photons is increased in turn and there are more
photons striking the metal surface.
Specifically, suppose we double the intensity of the light. Twice as many photons strike the metal
surface and knock out twice as many electrons—making a current that is twice as strong. In the
wave picture, however, you would expect that increasing the intensity would increase the energy
of the electrons, and not their number. Classical wave theory disagrees with observation.
The ideas of Planck and Einstein can be summarized by the Planck-Einstein relations.
DEFINITION: The Planck-Einstein Relations
The Planck-Einstein relations connect the particle-like properties of energy and momentum to
𝜔
wavelike properties of frequency and wave vector k. Recalling that frequency 𝜈 = 2𝜋

𝐸 = ℎ𝜈 = ℏ𝜔
𝑝 = ℏ𝑘
The Bohr Theory of the Atom
The Bohr Theory of the atom took into consideration the basic structure of the hydrogen atom. He
observed that the light emitted by isolated atoms takes the form of a discrete series of lines called
spectral lines. It was found that these lines occur at specific frequencies for type of atom. So a
sodium atom has a different line spectrum than a hydrogen atom, and a helium atom has yet another
spectrum. Think of a spectrum as the fingerprint of each element. It was also found that atoms
absorb light at specific, well-defined frequencies as well.
This tells us that like Planck’s blackbody oscillators, atoms can exchange energy only in fixed
discrete amounts. Neils Bohr noticed this and proposed two radical ideas about the behavior of
electrons in atoms.
The Two Key Assumptions of Bohr about the Atom are:
1. An electron can only orbit about the nucleus in such a way that the orbit is defined by the
relationship:
𝑚𝑣𝑟 = 𝑛ℏ, 𝑛 = 1, 2, . .. (8)
where v is the velocity of the electron, r is the radius of the orbit, and m is the mass of the electron.
The presence of n in the formula restricts the angular momentum of the electron to integer
multiples of ℏ, where the angular momentum is given by:
𝐿 = 𝑛ℏ (9)
2. Electrons only radiate energy during transitions between states. A transition from energy
state 𝐸𝑖 to energy state 𝐸𝑓 is accompanied by the emission of a photon of energy:
ℎ𝜈 = 𝐸𝑖 − 𝐸𝑓 (10)
The Coulomb force between the positively charged nucleus and the negatively charged electron is
what keeps the electrons in orbit. Setting this equal to the centrifugal force:
𝑒 2 𝑚𝑣 2
= (11)
𝑟2 𝑟
Results in the following expressions for the velocity of the electron and the radius of the orbit. We
label each quantity with subscript n to conform to assumption (1) above:
𝑒2
𝑣𝑛 = (velocity of electron in orbit 𝑛) (12)
𝑛ℏ
𝑛 2 ℏ2
𝑟𝑛 = (radius of electron in orbit 𝑛) (13)
𝑚𝑒 2
Example 1
Find the energy of an electron in the hydrogen atom using Bohr’s formulas.
Solution
We start by recalling that the
total energy = kinetic energy + potential energy = 𝑇 + 𝑉
For an electron moving in the Coulomb potential of a proton, the potential is just
𝑒2
𝑉=−
𝑟
Using the formula for the radius of orbit n this becomes:
𝑒2 𝑒2 𝑒2 𝑚𝑒 4
𝑉𝑛 = − = − 2 2 = − 2 2 𝑚𝑒 2 = − 2 2
𝑟𝑛 𝑛 ℏ 𝑛 ℏ 𝑛 ℏ
𝑚𝑒 2
For the kinetic energy, we obtain:
2
1 1 𝑒2 1 𝑚𝑒 4
𝑇 = 𝑚𝑣𝑛2 = 𝑚 ( ) =
2 2 𝑛ℏ 2 𝑛 2 ℏ2
The total energy of an electron in orbit n is therefore:
1 𝑚𝑒 4 𝑚𝑒 4 1 𝑚𝑒 4 2𝜋 2 𝑚𝑒 4
𝐸𝑛 = 𝑇𝑛 + 𝑉𝑛 = − =− 2 2=− 2 2
2 𝑛 2 ℏ2 𝑛 2 ℏ2 2𝑛 ℏ 𝑛 ℎ
Example 2
Derive a relation that predicts the frequencies of the line spectra of hydrogen.
Solution
Bohr proposed that the frequency of a photon emitted by an electron in the hydrogen atom was
related to transitions of energy states as:
ℎ𝜈 = 𝐸𝑖 − 𝐸𝑓
The energy of state n is:
2𝜋 2 𝑚𝑒 4
𝐸𝑛 = −
𝑛2 ℎ2
Therefore, let
2𝜋 2 𝑚𝑒 4
𝐸𝑖 = −
𝑛𝑖2 ℎ2
And
2𝜋 2 𝑚𝑒 4
𝐸𝑓 = −
𝑛𝑓2 ℎ2
Thus
2𝜋 2 𝑚𝑒 4 2𝜋 2 𝑚𝑒 4 2𝜋 2 𝑚𝑒 4 1 1
𝐸𝑖 − 𝐸𝑓 = − 2 2 + = ( − )
𝑛𝑖 ℎ 𝑛𝑓2 ℎ2 ℎ2 𝑛𝑓2 𝑛𝑖2
Putting this together with Bohr’s proposal we find the frequency is:
𝐸𝑖 − 𝐸𝑓 2𝜋 2 𝑚𝑒 4 1 1
𝜈= = 3
( 2 − 2)
ℎ ℎ 𝑛𝑓 𝑛𝑖
This formula can be used to predict the line spectra of hydrogen.
de Broglie’s Hypothesis
In 1923 Louis de Broglie proposed that the Planck-Einstein relations should be extended to
material particles. A particle with energy E is associated with a wave of frequency 𝜔 = 𝐸/ℏ. In
addition, momentum is related to the wave vector via 𝒑 = ℏ𝒌. Applying these simple relations to
material particles like electrons, de Broglie proposed that a material particle moving with
momentum p has a wavelength:
ℎ ℎ
𝜆= =
𝑝 𝑚𝑣
If a particle of mass m is moving with a nonrelativistic energy E, we can write:
ℎ
𝜆=
√2𝑚𝐸
Example 3
Find the de Broglie wavelength of an electron with a velocity of 107 m/s. The rest mass of an
electron is 𝑚0 = 9.1 × 10−31 kg.
Solution
Since 𝑣 << 𝑐, we can let 𝑚 = 𝑚0 . Hence
ℎ 6.6 × 10−34
𝜆= = = 7.3 × 10−11 𝑚
𝑚𝑣 9.1 × 10−31 × 107

The radius of the hydrogen atom is 5.3 × 10−11 𝑚. The de Broglie wavelength of the electron
(with a velocity of 107 m/s) is comparable with the dimensions of atoms. Therefore, the wave
character of moving electrons is the key to understanding atomic structure and behavior.