Origin and Development of Quantum Mechanics

By; Bessie M

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Quantum Mechanics
→ Quantum mechanics, science dealing with the behavior of 𝑚𝑎𝑡𝑡𝑒𝑟 and
𝑙𝑖𝑔𝑕𝑡 on the atomic and subatomic scale.
→ It attempts to describe and account for the properties of molecules and
atoms and their constituents- electrons, protons, neutrons...etc.
→ These properties include the interactions of the particles with one another
and with electromagnetic radiation (i.e., light, X-rays, and gamma rays).
 The study of quantum mechanics is rewarding for several reasons.
 First, it illustrates the essential methodology of physics.
 Second, it has been enormously successful in giving correct results in
practically every situation to which it has been applied.

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Classical physics - (pre 1900)
• Mechanics – Newton
• Thermodynamics - Boltzmann, Gibbs et al.
• Electromagnetics - Maxwell et al.
Scientists believed that:
 The physical universe was deterministic.
 Light consisted of waves, where as ordinary matter was
composed of particles.
 Physical quantities (energy, momentum,…etc.) could be
treated as continuous variables.
 There exists an objective physical reality independent of any
observer.

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Outstanding problems c. 1900

Planck Einstein Bohr

Black-body radiation The nature of light The structure of the atom

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• There are three ways that light interacts with matter:

 In principle, all three things can be happening simultaneously. However, we see most
things through reflection.
 If an object has no reflection, then, if there is no generation, it would appear to be
absolutely black. We call it a black-body. All incident light is totally absorbed.

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Black-body radiation spectrum
→ As the BB is heated, the total energy emitted increases (obviously)
and the peak in the spectrum shifts to higher frequencies (shorter
wavelengths).

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 The properties of black-body radiators had been determined experimentally by the end of
the 1800s.
→ The total 𝐸𝑀 power (integrated over all frequencies) radiated by a black body at a given
temperature 𝑇 is

𝑃 = 𝜍𝐴𝑇 4 (𝑆𝑡𝑒𝑓𝑎𝑛 − 𝐵𝑜𝑙𝑡𝑧𝑚𝑎𝑛𝑛 𝑙𝑎𝑤. )

where 𝐴 is the surface area of the BB and 𝜍 is a constant equal to 5.67 × 10−8 𝐽/𝑠𝑚2 𝐾 4

→ However, since we usually work with a cavity, we can say the same thing by looking at the
total 𝐸𝑀 energy density within the cavity.
∞
𝜌𝑇 = 𝜌 𝑣 𝑑𝑣 ⟹ 𝜌𝑇 = 𝑎𝑇 4
0

where the constant 𝑎 is equal to 5.67 × 10−8 𝐽/𝑚3 𝐾 4

→ Lastly, the peak frequency increases linearly with temperature, meaning that wavelength
is inversely proportional to temperature.
𝒲 The experimental facts weren’t in dispute.
𝜆𝑝𝑒𝑎𝑘 = (𝑇𝑕𝑖𝑠 𝑖𝑠 𝑊𝑖𝑒𝑛’𝑠 𝐿𝑎𝑤)
𝑇 These results had been measured in
many laboratories by 1900.
where 𝒲 = 2.90 × 10−3 𝑚. 𝐾.w
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 Trouble came though when theorists tried to explain the BB spectrum. This should have
been a 𝑠𝑡𝑟𝑎𝑖𝑔𝑕𝑡 − 𝑓𝑜𝑟𝑤𝑎𝑟𝑑 application of thermodynamics and 𝐸𝑀 theory.

 Use electromagnetics to determine the electromagnetic modes inside the cavity.

 Use thermodynamics to determine the distribution of energy
 Underlying it all is the assumption that all energies are possible (a continuous
distribution of energies).
The expression obtained using the classical theories was
8𝜋𝜅𝑇 2
𝜌 𝑣 = 𝑣
𝑐3
 Comparing the theoretical equation to the experimental results showed that the theory
was a miserable failure.
 In fact, it predicted an infinite amount energy being radiated! (Referred to as the
“ultraviolet catastrophe.”

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In 1900, Max Planck proposed a way to derive a suitable equation.

To get there, he tossed aside the assumption that energies are continuously distributed.
Instead assumed that the energy of EM modes in the cavity consisted of discrete packets. The
energy of each packet was proportional to the frequency of the 𝐸𝑀 mode.
𝐸 = 0, 𝑕𝜈, 2𝑕𝜈, 3𝑕𝜈, 4𝑕𝜈, 5𝑕𝜈, 𝑒𝑡𝑐.

With this modification, the Planck’s result was

8𝜋𝑕 𝑣3
𝜌 𝑣 = 3 ×
𝑐 𝑕𝑣
𝑒𝑥𝑝 −1
𝜅𝑇
This matched the experimental results exactly, if 𝑕 was chosen to have a value of
6.63 × 10−34 𝐽.
This was the first use of the notion of quantization of energy.

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Light quantum /light Quanta/
 The quantum of light is called a “photon”. Photons are the particles
of light. Light is made of photons. That's what it means to say that
light is quantized.
 A new interpretation of the emission of light by heated objects and
new experimental methods that opened the atomic world for study
led to a radical departure from the classical theories of Newton and
Maxwell—quantum mechanics was born. Once again the question
of the nature of light was reopened.

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1) The photoelectric effect — the nature of light
 The ejection of electrons from a metal surface by light is called the
photoelectric effect.
 An experiment by Philipp Lenard showed that the energy of the
detached electrons is given by the frequency of the irradiating
light.
 Monochromatic light yields electrons of a definite energy.
 If we carry out the experiment with monochromatic light of
different frequency, a linear dependence between energy and
frequency is obtained,

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Observations on photoelectric effect
1) Rate of emission of photoelectrons proportional to intensity of
incident electromagnetic radiation
2) Maximum Kinetic Energy of the photoelectron is independent of
intensity of incident electromagnetic radiation and depend
linearly on frequency of 𝐸𝑀 radiation.
A plot of 𝐸𝑚𝑎𝑥 𝑣𝑒𝑟𝑠𝑢𝑠 𝑓𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦looked nearly the same for
all metals used for the emitting electrode. Different metals
would result in different minimum frequencies, but otherwise
the curves were identical.
The proportionality factor, i.e. the slope of the straight line, is
found to be Planck's constant 𝑕 divided by 2𝜋, so that,
𝐸~ 𝑎 + 𝑏𝑣
𝐸 = ℏ 𝜔 − 𝜔0 = 𝑕 𝑣 − 𝑣0 With 𝑕 = 2𝜋ℏ = 6.6 × 10−34 𝑊𝑠 2
The second of these is puzzling, since according to classical 𝐸𝑀 theory, the frequency
should play no role in the describing the energy transfer from light to electrons.

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→ Before quantum mechanics –According to Kirchhoff: The amount of radiation being
absorbed at each and every frequency, will be exactly matched by outgoing radiation
generated by the BB.
→ However, the black-body can generate light. In fact, it must in order to maintain
equilibrium.

→ According to Kirchhoff: The amount of radiation being absorbed at each and every
frequency, will be exactly matched by outgoing radiation generated by the BB.
So, a perfect absorber of light must also be a perfect emitter of light.

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Einstein (1905)
 Following Planck’s lead, Einstein postulated that the EM energy was
carried in discrete packets of size 𝐸 = 𝑕𝑣.
 Essentially, he was saying that in the photoemission experiment,
the light came in the form of particles, which would later come to
be called photons.
 The electrons are bound in the metal and a certain minimum
energy is required to break them free called work function
Φ 𝑜𝑟 𝐸𝐵 .
𝜙 = 𝐸𝐵 = 𝑕𝑣
o This “binding” energy is different for different metals.

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Energy of photon
 Electrons emitted from underneath the metal surface lose some
kinetic energy during the collision. But the surface electrons carry
all the kinetic energy imparted by the photon and have the
maximum kinetic energy.
𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑝𝑕𝑜𝑡𝑜𝑛
= 𝑒𝑛𝑒𝑟𝑔𝑦 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑡𝑜 𝑒𝑗𝑒𝑐𝑡 𝑎𝑛 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 (𝑤𝑜𝑟𝑘 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛)
+ 𝑀𝑎𝑥𝑖𝑚𝑢𝑚 𝑘𝑖𝑛𝑒𝑡𝑖𝑐 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑡𝑕𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛
𝐸 = 𝑕𝑣 = 𝐾. 𝐸𝑚𝑎𝑥 + Φ
⟹ 𝐾. 𝐸𝑚𝑎𝑥 = 𝑕𝑣 − Φ

At the threshold frequency, 𝜈0 electrons are just ejected and do not have any kinetic energy.
Below this frequency, there is no electron emission. Thus, the energy of a photon with this
frequency must be the work function of the metal.
𝑊 = Φ = 𝑕𝑣0

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Maximum kinetic energy
Thus, Maximum kinetic energy equation becomes:
1
𝐾. 𝐸𝑚𝑎𝑥 = 𝑚𝑣 2 𝑚𝑎𝑥 = 𝑕𝑣 − 𝑕𝑣0 = 𝑕 𝑣 − 𝑣0
2
𝐾. 𝐸𝑚𝑎𝑥 calculated experimentally using the stopping
potential.
1
𝑠𝑡𝑜𝑝𝑖𝑛𝑔 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 = 𝑒𝑣0 = 𝑚𝑣 2 𝑚𝑎𝑥
2

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wave-particle duality
 𝐸𝑀 radiation can have a dual nature.
 In some cases, it behaves like a wave (reflection,
refraction, diffraction, etc.) and sometimes it manifests
itself as a particle, the photon, with energy 𝐸 = 𝑕𝑣.

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Photon momentum
 If the photon is a particle with a known energy, it must have some
momentum associated with it.
 We can’t calculate the momentum using Newtonian mechanics,
because the photon has no mass. (From Einstein’s Theory of
Special Relativity), the only way that a particle like a photon can
move at the speed of light is if it has no mass.
 From special relativity, the momentum of the photon can be
obtained from the total energy of a particle as
𝐸 2 = 𝑃2 𝑐 2 + 𝑚0 2 𝑐 4
where 𝑐 is the speed of light, 𝑝 is the momentum and 𝑚0 is the rest
mass of the photon.

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Since the photon mass is zero, the second term on the right is zero, leaving

𝐸 2 = 𝑃2 𝑐 2

𝑕𝑐
⟹𝐸= = 𝑃𝑐
𝜆
ℎ
𝜆 = (de-Broglie wavelength)
𝑃

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Examples
1) A radiation of wavelength 300 nm is incident on a silver surface.
Will photoelectrons be observed? The work function of silver = 4.7
eV
𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛
ℎ𝑐 6.626×10−34 ×3×108
𝐸= = = 6.63 × 10−19 𝐽 = 4.14 𝑒𝑣.
𝜆 300×10−9
𝐸𝑥𝑝𝑙𝑎𝑛𝑎𝑡𝑖𝑜𝑛
Since the energy of the incident photon is less than the work function
of silver, photoelectrons are not observed in this case.

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Exercise
The work function of potassium is 2.30 𝑒𝑉. UV light of wavelength
𝑊
3000 Å and intensity 2 2 is incident on the potassium surface.
𝑚
i) Determine the maximum kinetic energy of the photo electrons
ii) If 40% of incident photons produce photo electrons, how many
electrons are emitted per second if the area of the potassium
surface is 2 𝑐𝑚2 ?

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Solutions
The power per area is
𝑃 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝ℎ𝑜𝑡𝑜𝑛𝑠
= × 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑡𝑕𝑒 𝑝𝑕𝑜𝑡𝑜𝑛
𝐴 𝑡𝑖𝑚𝑒×𝑎𝑟𝑒𝑎 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑒𝑡𝑎𝑙

Rearranging,
𝑃
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑕𝑜𝑡𝑜𝑛𝑠 =
𝐸𝐴
ℎ𝑐 6.626×10−34 ×3×108
i) 𝐸= = = 6.626 × 10−34 𝐽 = 4.14 𝑒𝑉
𝜆 3000×10−10
𝐾. 𝐸𝑚𝑎𝑥 = 𝐸 − Φ0 = 1.84 𝑒𝑉
ii) The number of photons reaching the surface per second
𝑃 2
𝑛𝑝 = = = 6.04 × 1014 𝑝𝑕𝑜𝑡𝑜𝑛𝑠/𝑠𝑒𝑐𝑜𝑛𝑑
𝐸𝐴 6.626×10−19 2×10−4
Rate of emission of photo electrons=40%𝑛𝑝
⟹ 𝑟𝑎𝑡𝑒 𝑜𝑓𝑒𝑚𝑖𝑠𝑠𝑖𝑜𝑛 = 0.4 × 6.04 × 1014 = 2.415 × 1014 𝑝𝑕𝑜𝑡𝑜𝑛𝑠/𝑠𝑒𝑐

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1.3. The Bohr Atomic Model/The structure of the atom
→ The atom was viewed as a miniature/very small/ solar system: a
massive, positively charged nucleus (analogous to the sun) with the
negatively charged electrons orbiting around it (similar to the planets.)
The two parts are held together by the electrostatic attraction between
the charges.
→ This was an appealing picture because the attractive electrostatic
force has the same 𝑟 −2 dependence as the force of gravity that attracts
the planets to the sun.
→ From a classical point of view, we might expect the electrons to
move in stable orbits with a continuous range of energies, angular
momenta, and orbital sizes possible.

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 → There are two major problems with the “atom-as-a-solar-system” picture.
o First, 𝐸𝑀 theory tells us that an accelerating electron will give off radiation (emit photons)
and lose energy.
 Since an electron moving in a classical orbit around a nucleus is under constant centripetal
acceleration, it should give off a continuous stream of photons and continually lose energy.
As the electron loses energy, it would spiral down until it eventually crashes into the
nucleus. The classical picture leads to atoms that are not stable!

o The second problem is that when one looks at the optical emission form of atoms, there is
not a continuous range of frequencies being emitted. Instead the emission is bunched
into very specific, discrete “lines”.

Hydrogen emission spectra in the visible (400 nm - 700 nm).

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→There were other collections of lines in the UV and IR, that were measured later (Lyman
series, Paschen series, Brackett series).
→ The spectrum from hydrogen atoms shown previously is known as the “Ballmer series” of
lines. The spectra was measured in the 1800s.
Rydberg was able to come up with a totally empirical formula describing the position of the
lines in the Ballmer series.

1 1 1
=R −
𝜆 𝑛2 2 𝑛1 2

where R is a constant (the Rydberg) = 1.097 × 107 /m and 𝑛1 is an integer greater

than 𝑛2 .

Taking the experimental results and tying them to some of the nascent quantum
ideas, Niels Bohr managed to patch together a theory that seemed to account for
the observed optical properties of the hydrogen atom.

Hydrogen was used as the standard, since it was the simplest atom, with just a single
electron. Also, it’s emission properties were will known from many experiments.

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 Balmer series
The Balmer series is the name given to a series of spectral emission lines of the hydrogen
atom that result from electron transitions from higher levels down to the energy level with
principal quantum number 2
The Balmer series of transitions is labeled using Greek characters with 𝛼 representing
Δ𝑛 = 1, 𝛽 representing Δ𝑛 = 2, etc; the first four transitions are as follows:

Because hydrogen is the most abundant element in the Universe, the Balmer lines are a
common feature in optical astronomy and the red 𝐻𝛼 line corresponding to the electron
transition from the 𝑛 = 3 to the 𝑛 = 2 energy level gives the characteristic pink/red color in
true-color images of ionized regions in planetary nebulae, supernova remnants and stellar
nurseries.

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Bohr used the quantization ideas of Planck and the picture of photons
provided by Einstein. Here are the elements of his model:

1) The electron in a hydrogen atom moves in circular orbit about the proton (nucleus) under
the influence of the Coulomb attraction, obeying the laws of classical mechanics.

2) Instead of the infinity of orbits which should be possible, electrons instead are limited to
orbits for which the angular momentum is quantized in multiples of 𝑕/2𝜋 (hereafter
denoted as ℏ ). This says that angular momentum, 𝐿 = 𝑚𝑣𝑟 = 𝑛ℏ where 𝑚 is the electron
mass, 𝑣 is the velocity, 𝑟 is the radius of the orbit, and 𝑛 is an integer (𝑞𝑢𝑎𝑛𝑡𝑢𝑚 𝑛𝑢𝑚𝑏𝑒𝑟).
These specific orbits are called orbitals.
3) Even though the electron is being accelerated constantly in an orbit, it does not emit any
EM radiation.
4) EM radiation is emitted if the electron changes from one orbit to another, i.e. from one
energy level to another.

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The difference in energy is given off as a photon with

𝐸𝑖 − 𝐸𝑓 = 𝑕𝑣
where 𝐸𝑖 is the initial orbital energy and 𝐸𝑓 is the final energy

Bohr’s approach was a hybrid theory, mixing classical ideas with the new quantum concepts,
but did seem to explain the observed optical spectra.

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The radius and the energy of a Bohr orbital in the hydrogen atom can
be calculated. (These are purely classical calculations.)
To find the radius, we set the Coulomb force equal to the centripetal
force. 2 2
𝑞 𝑚𝑣
𝐹𝑒 = 𝐹𝑐 ⟹ 2
=
4𝜋𝜀0 𝑟 𝑟
where 𝑞 is the charge of one electron and 𝜀0 is the free-space permittivity.
Using the above relation together with the angular momentum quantization condition,

𝐿 = 𝑚𝑣𝑟 = 𝑛ℏ
Solving for the radius 𝑟
4𝜋𝜀0 ℏ2 2
𝑟= 2 𝑛
𝑞 𝑚
For 𝑛 = 1, the radius works out to 0.0531𝑛𝑚 , which is known as the “Bohr radius”, and
denoted as 𝑎0 .

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→ To find the energy of the electron in an orbit, we add the kinetic and potential energies.
1 2
𝑞2
𝐸 = 𝐾. 𝐸 + 𝑃. 𝐸 = 𝑚𝑣 −
2 4𝜋𝜀0 𝑟
→ (Since the potential is attractive between nucleus and electron, the potential
energy-term will be negative. We are assuming that 𝐸 = 0 when the electron is infinitely
far away from the nucleus. This leads to the orbital energies being negative.)
∗ Inserting the expression for the quantized angular momentum and the radius found on
the previous page gives
𝑛ℏ 2 𝑛 2 ℏ2 4𝜋𝜀0 ℏ2 2
𝑣= ⟹𝑣 = and 𝑟 = 𝑛
𝑚𝑟 𝑚2 𝑟 2 𝑞2 𝑚

𝑚𝑞 4 1
𝐸=−
2 4𝜋𝜀0 2 ℏ2 𝑛2
Plugging in for the constants within the brackets:

−13.6 𝑒𝑉
E=
𝑛2

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→ The lowest possible energy is Energy levels in Bohr atom
given by 𝐸1 .
→ This is known as the “ground
state”.
→ Since the electron cannot drop
below this, the atom is stable.
→ The energy transitions must have
energies given by:
1 1
𝐸 = 13.6 𝑒𝑉 −
𝑛𝑓 2 𝑛𝑖 2

where 𝑛𝑓 and 𝑛𝑖 are integers, with 𝑛𝑖 > 𝑛𝑓

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 1 1
𝐸 = 13.6 𝑒𝑉 −
𝑛𝑓 2 𝑛𝑖 2

Note this expression agrees with the empirical relationship determined by Rydberg from the
experimental spectra.
ℎ𝑐 1 1 1 2.17×10−18 𝐽 1 1 1 1
𝐸= = 13.6 𝑒𝑉 − ⟹ = − ≡𝑅 −
𝜆 𝑛𝑓 2 𝑛𝑖 2 𝜆 ℎ𝑐 𝑛𝑓 2 𝑛𝑖 2 𝑛𝑓 2 𝑛𝑖 2

Bohr’s model of the atom matched well with the experimental observations.
We’ve seen 3 important problems that required new, unusual notions to be added
to the familiar theories of classical physics.

 black-body radiation → quantization of energy

 photoelectric effect → light as a particle
 hydrogen atom emission spectra → quantization of atomic orbits
In addition, 𝑑𝑒 − 𝐵𝑟𝑜𝑔𝑙𝑖𝑒 added an extra wrinkle by proposing that if light can
behave like a particle, then particles might behave like waves.
These were all intriguing ideas, but they did not constitute a coherent theory that could be
applied to new problems. Something more fundamental was needed. So the next step to
come was the development of a true quantum theory based on the Schrödinger equation.

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1.4. Limitations of Classical Mechanics
Classical mechanics is the mathematical science that studies the displacement of
bodies under the action of forces.
1) Unable to explain a host of experimental observations
2) A second limitation on the validity of Newtonian mechanics appeared at the
microscopic length scale.
Einstein, by insisting on a fundamental rethinking of the concepts of space and
time, and the relativity of motion, in his special theory of relativity (1905) was able
to resolve the apparent conflicts between optics and Newtonian mechanics.
In particular, special relativity provides the necessary framework for describing the
motion of rapidly moving objects (speed greater than 𝑣 > 0.1𝑐 ).

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 1.5. Development of Quantum mechanics
→ The development of quantum mechanics meant for those four “certainties” of
classical physics:
Classical Modern
The physical universe is deterministic. The physical universe is not deterministic. At the
scale of atomic particles, the best that we can do
is find the probability of the outcome of an
experiment. We can’t predict exact results with
certainty. Uncertainty is an intrinsic property of
matter at this level.
Light consists of waves, while ordinary matter is Both light and matter exhibit behavior that seems
composed of particles. characteristic of both particles and wave. (wave-
particle duality)
Physical quantities (energy, momentum, etc.) can Under certain circumstances, some physical
be treated as continuous variables. quantities are quantized, meaning that they
can take on only certain discrete values.

There exists an objective physical reality It appears that the observer always affects
independent of any observer. the experiment. It is impossible to
disentangle the two.
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By the early part of the twentieth century, quantum
mechanics provided a mathematical description of
microscopic phenomena in complete agreement with our
empirical knowledge of all non-relativistic phenomena.
→ Non-relativistic refers to-not based on or involving the theory of relativity

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