ODA BULTUM UNIVERSITY

COLLEGE OF NATURAL AND

COMPUTATIONAL SCIENCE
DEPARTMENT OF PHYSICS

NOTE OF QUANTUM MECHANICS I

BY MOHAMMED K. (PhD)
Year, 2024
 CHAPTER ONE

1. Origin and Development of Quantum Mechanics

• Limitations of Classical Mechanics
• The need for quantum mechanics
• Development of Quantum Mechanics
• Wave/Particle Dualism
• Postulates of quantum mechanics
• Schrödinger equation
INTRODUCTION:
• Quantum mechanics is a physical science dealing with the behavior of matter and energy
on the scale of atoms and subatomic particles or waves.
Classification in Physics
Limitations of Classical Mechanics
• Here are key limitations of classical mechanics OR significant differences between
classical mechanics and quantum mechanics:
1. Quantization of Energy:
- In CMs, energy can take on any continuous value.
- In QMs, energy is quantized, meaning that it can only be absorbed or emitted in
discrete, specific amounts or "quanta."
2. Bohr's Model of the Atom:
- The Bohr model of the atom, which is based on quantum mechanics, states that
electrons can only occupy certain discrete energy levels within an atom.
- Transitions between these energy levels result in the emission or absorption of a specific
amount of energy, corresponding to the difference between the energy levels.
3. Blackbody Radiation - an idealized “blackbody” is a material object that absorbs all
of the radiation falling on it.
- CM, using the laws of thermodynamics, failed to explain the observed spectrum of
blackbody radiation, which is the electromagnetic radiation emitted by a perfect
absorber of light. These predicted infinite brightness at low wavelength (i.e. high
frequencies), a prediction called ultraviolet catastrophe.
- This theoretical problem solved by Max Planck, who had to assume that
electromagnetic radiation could propagate only in discrete packets, or quanta. This
idea later used by Einstein to explain the photoelectric effect.
- The total intensity Or the total power per unit surface area radiated by bb at a given
temp.T is given by; 𝐼𝑖𝑛𝑡 = 𝑎𝛿 𝑇 4 , (is called Stefan -Boltzann law).
- Wien’s energy density distribution: Using thermodynamic arguments, Wien took the
Stefan–Boltzmann law he extended it to obtain the energy density per unit frequency
of the emitted blackbody radiation: 𝑢 𝑣, 𝑇 = 𝐴𝑣 3 𝑒 −𝛽𝑣/𝑇 . where A and 𝛽; are
empirically defined parameters.
Although Wien’s formula fits the high-frequency data remarkably well, it fails
badly at low frequencies.
Rayleigh’s energy density distribution
• the electromagnetic energy density in the frequency range 𝑣 𝑡𝑜 𝑣 + 𝑑𝑣 is given
𝑣2
by, 𝑢 𝑣, 𝑇 = 8𝜋 3 𝐾𝑇. ………….(*)
𝑐
• Except for low frequencies, this law is in complete disagreement with
experimental data: u(v, T) as given by (*) diverges for high values of v.
• this was called the ultraviolet catastrophe, for (*) diverges for high frequencies
(i.e., in the ultraviolet range)—a real catastrophically failure of classical physics.
- Planck's quantum hypothesis, which introduced the concept of energy
quantization, was able to successfully explain the blackbody radiation spectrum.
- The energy of a packet was proportional to the frequency (𝑣) of the EM mode .
- It is given by; 𝐸𝑛 = 𝑛ℎ𝜈, where, n = 0, 1, 2, 3,….
- with this modification Planck's energy density was,
8𝜋ℎ 𝑣 3
𝑢 𝑣 = 3
𝑐 𝑒 ℎ𝑣β − 1
- where, 𝛽 = 1/𝐾𝑇.
4. Photoelectric Effect:
- The photoelectric effect, where electrons are emitted from a metal surface when
it is illuminated by light, cannot be explained by classical mechanics.
- Einstein's explanation of the photoelectric effect, based on the concept of light
being composed of discrete quanta (photons), was a crucial step in the
development of quantum mechanics.
- Minimum energy required to remove electrons from the metal surface is work
function (𝜑).
• He assumed light to be consisting of discrete quanta (photons), each of energy hν, ν being the frequency of
light. When a metal is irradiated by light, an electron absorbs a photon (a quantum of energy) and gains an
amount of energy equal to hν irrespective of the intensity of the falling light. If this amount of energy is greater
than the work function of the metal, the electron will be ejected.
• If the amount of energy is not greater than the work function of the metal, the electron will not be able to
overcome the potential barrier.
• Therefore, the photoelectric effect can take place only if hν ≥ 𝜑.
• As a result, Einstein’s fundamental equation for photoelectric effect reads:
• hν = K.Emax+ 𝜑 𝑜𝑟 𝐾. 𝐸𝑚𝑎𝑥 = ℎ𝑐/𝜆 − 𝜑
• deBroglie postulate
— Is the EM radiation wave or particle?
— It seems that EM radiation can have dual-nature.
— In some cases it behaves like waves (reflection, refraction, etc)and sometimes it manifests itself as a packets, the
photon, with energy, 𝐸 = ℎ𝜈.
• The postulates says;-The property of wave particle duality of light is also a property of all other matter with
mass, 𝑚 ≠ 0.
⸺ is deBroglie relation.
Thus, EM radiation exhibits dual nature of light.
• Properties of photoelectric effect: If the frequency of the incident radiation is
smaller than the metal’s threshold frequency—no electron can be emitted
regardless of the radiation’s intensity (frequency that depends on the properties of
the metal).
• No matter how low the intensity of the incident radiation, electrons will be ejected
instantly the moment the frequency of the radiation exceeds the threshold
frequency 𝑣0 .
• At any frequency above 𝑣0 , the number of electrons ejected increases with the
intensity of the light but does not depend on the light’s frequency.
• The kinetic energy of the ejected electrons depends on the frequency but not on
the intensity of the beam; the kinetic energy of the ejected electron increases
linearly with the incident frequency.
• These experimental findings cannot be explained within the context of a purely
classical picture of radiation, notably the dependence of the effect on the threshold
frequency.
• The Photoelectric Effect: It was experimentally established that irradiation of metallic surfaces with light led to
the ejection of electrons. This phenomenon of ejection of electrons from a metallic surface under the action of
light is known as photoelectric effect.
• The phenomenon had some peculiar properties: (a) when the frequency of the irradiating light was less than the
so-called threshold frequency (𝑣0 ), irrespective of the intensity of the irradiating light, no electrons could be
ejected, (b) irrespective of the intensity of radiation (high or low) electrons were ejected instantaneously
provided the frequency of radiation was greater than the threshold frequency and (c) the kinetic energy of the
ejected electrons depended on the frequency but not on the intensity of the irradiating light. Note that the
threshold frequency is a characteristic of a given metal and is defined as 𝑣0 = 𝜑 /h, where Φ is the work function
of the metal and h Planck’s constant. The work function is the minimum energy required for an electron to
overcome the attractive forces that bind it to the metal surface. The dependence of the photoelectric effect on the
frequency of the falling radiation, which must be greater than the threshold frequency, could not be explained in
the framework of classical physics.
• According to classical wave theory of light, the intensity of light is proportional to the square of the amplitude of
the oscillating electric field. Hence, light of any frequency with sufficient intensity should be able to supply the
required amount of energy for the electrons to overcome the potential barrier (work function) and become free.
However, this was not the case in reality.
• The second important point was the instantaneous ejection of electrons from the surface. According to classical
physics, even if the falling radiation is weak, the electron would continuously absorb energy from it and in the
process would be able to accumulate enough energy to leave the surface of the metal. Hence, according to
classical physics, if the radiation is weak, the photoelectric effect should take some time before it shows up.
However, no detectable time lag has ever been measured.
5. Energy Levels and Transitions:
- In QMs, the energy of a system, such as an atom or a molecule, is confined to
specific, discrete energy levels.
- Transitions between these energy levels occur through the absorption or emission
of a specific amount of energy, corresponding to the difference between the
energy levels.
- This is in contrast with CMs, where energy can take on any continuous value.
6. Energy Conservation and Uncertainty:
- In CMs, energy is always conserved, and the precise values of energy and other
physical quantities can be determined.
- In QMs, the uncertainty principle implies that the precise values of certain pairs
of physical quantities, such as energy and time, cannot be determined
simultaneously with arbitrary precision.
The need for quantum mechanics
• The need for quantum mechanics arises from the limitations of classical
mechanics in describing the behavior of matter and energy at the atomic and
subatomic scales.
• Quantum mechanics is a fundamental theory in physics that provides a more
comprehensive understanding of the physical world, particularly in the realm of
the very small.
Here are some of the key reasons why quantum mechanics is necessary:
1. Explanation of atomic and subatomic phenomena:
- Classical mechanics fails to explain the behavior of atoms, molecules, and
subatomic particles, such as electrons, protons, and neutrons.
- Quantum mechanics is essential for understanding the structure of atoms, the
nature of chemical bonds, and the behavior of subatomic particles.
2. Wave-particle duality:
- Quantum mechanics introduces the concept of wave-particle duality, where particles
exhibit both wave-like and particle-like properties.
- This is in contrast with classical mechanics, which treats particles as localized, point-like
objects.
3. Uncertainty principle:
- The uncertainty principle, a fundamental principle of quantum mechanics, states that
there is a fundamental limit to the precision with which certain pairs of physical
properties, such as position and momentum, can be known simultaneously.
- This principle has profound implications for our understanding of the behavior of
microscopic systems.
4. Quantum tunneling:
- Quantum mechanics explains the phenomenon of quantum tunneling, where particles can
penetrate through potential energy barriers that they would not be able to overcome
according to classical mechanics.
- This effect has important applications in semiconductor devices and nuclear physics.
5. Quantum computing and information:
- Quantum mechanics is the foundation for the emerging field of quantum
computing, which promises to revolutionize information processing by exploiting
the unique properties of quantum systems.
- Quantum mechanics also underpins the field of quantum information, which
explores the storage, manipulation, and communication of information using
quantum systems.
6. Explaining the properties of matter:
- Quantum mechanics is essential for understanding the properties of materials, such
as their electrical, magnetic, and optical properties, which are determined by the
behavior of electrons in atoms and molecules.
- Without quantum mechanics, we would not be able to explain the existence of
superconductors, semiconductors, and many other important materials.
Development of Quantum Mechanics
• The development of quantum mechanics is a fascinating and pivotal chapter in the
history of physics.
• It emerged in the early 20th century as a response to the limitations of classical
mechanics in explaining certain phenomena observed at the atomic and subatomic
scales.
 Historically, there were two independent formulations of quantum mechanics.
 The first formulation, called matrix mechanics, was developed by Heisenberg (1925) to
describe atomic structure starting from the observed spectral lines
 The second formulation, called wave mechanics, was due to Schrödinger (1926); it is a
generalization of the de Broglie postulate.
 This method, more intuitive than matrix mechanics, describes the dynamics of microscopic
matter by means of a wave equation, called the Schrödinger equation; instead of the matrix
eigenvalue problem of Heisenberg, Schrödinger obtained a differential equation.
 These two supposedly different formulations—Schrödinger’s wave formulation and
Heisenberg’s matrix approach—were shown to be equivalent.
Dirac then suggested a more general formulation of quantum mechanics which
deals with abstract objects such as kets (state vectors), bras, and operators.
The representation of Dirac’s formalism in a continuous basis—the position or
momentum representations—gives back Schrödinger’s wave mechanics.
• The key milestones in the development of quantum mechanics include:
 Planck's Quantum Hypothesis (1900):
-Max Planck proposed that energy is emitted and absorbed in discrete packets or
quanta, rather than continuously, in order to explain the observed properties of
blackbody radiation.
-This was a crucial first step towards the development of quantum theory.
 Einstein's Explanation of the Photoelectric Effect (1905):
-Albert Einstein explained the photoelectric effect, where electrons are emitted
from a metal surface when it is illuminated by light, by proposing that light itself
is composed of discrete quanta, later called photons.
- This further reinforced the idea of the quantization of energy.
 Bohr's Model of the Atom (1913):
- Niels Bohr proposed a model of the atom, where electrons could only occupy certain discrete energy levels, and the transition
between these levels resulted in the emission or absorption of specific amounts of energy.
- This model was a significant step towards a quantum mechanical description of atomic structure.
 Compton effect: - in 1923 Compton made an important discovery that gave the most conclusive confirmation for the
corpuscular aspect of light. This was contrary to the classical theory of radiation according to which the incident and the
scattered radiations should have the same wavelength.
 The increase in the wavelength of X-rays after scattering off a free electron is known as Compton effect.
- By scattering X-rays with electrons, he confirmed that the X-ray photons behave like particles with momenta hv/c; v is the
frequency of the X-rays.
 Wave-Particle Duality:
- Louis de Broglie proposed that not only light, but also matter, exhibits both wave-like and particle-like properties.
- This concept of wave-particle duality was later experimentally confirmed, laying the foundation for the development of a
comprehensive quantum theory.
 Heisenberg's Uncertainty Principle (1927):
- Werner Heisenberg formulated the uncertainty principle, which states that there is a
fundamental limit to the precision with which certain pairs of physical properties, such as
position and momentum, can be known simultaneously.
 Schrödinger's Wave Equation (1925):
- Erwin Schrödinger developed a wave equation that could describe the behavior of
quantum mechanical systems.
- This equation, along with the Copenhagen interpretation of quantum mechanics,
provided a comprehensive mathematical framework for quantum theory.
Wave/Particle Dualism
a. wave properties of particle b. particle properties of wave
• Interference • Photoelectric effect,
• Diffraction • Blackbody Radiation,
• Or Davisson–Germer, • Compton effect,
Thomson, and double-slit experiments • pair production, exhibits particle-like
exhibits wave-like characteristics. characteristics.

— both (a,b) reveal that photons, electrons, and any other microscopic particles behave
unlike classical particles and unlike classical waves.
o at the microscopic scale, nature can display particle behavior as well as wave
behavior.
o This dual behavior can in no way be reconciled within the context of classical physics,
for particles and waves are mutually exclusive entities.
 The theory of QMs, provides the proper framework for reconciling the particle and
wave aspects of matter.
 it can simultaneously make statements about the particle and wave behavior of
microscopic systems by using a wave function /state vector.
 It combines the quantization of energy or intensity with a wave description of matter.
 That is, it uses both particle and wave pictures to describe the same material particle.
 Microscopic systems, thus, are neither pure particles nor pure waves, they are both.
 The particle and wave manifestations do not contradict or preclude one another, but,
as suggested by Bohr, they are just complementary.
 Both concepts are complementary in describing the true nature of microscopic
systems.
 Postulates of quantum mechanics
Postulate 1: The Quantum State
State of a system can be described by a function Ψ.
• This function is called state function or state vector.
• Is a function of a generalized coordinates and time , Ψ(ȓ, t).
Properties of wave function
• Ψ should satisfy the law of conservation of energy i.e 𝐻 = 𝑃𝐸 + 𝐾𝐸
• be consistent with de Broglie hypothesis i.e λ = h/p
• be single valued ( because probability is unique)
• be continuous
• be finite
• be linear so that de Broglie waves have the important superposition property.
The form and development in time of the state are determined by the time-dependent
dΨ(x, 𝑡)
Schrödinger equation (TDSE): iħ = ĤΨ(x, 𝑡)……..(1)
dt
where Ψ is the quantum state and Ĥ is the Hamiltonian operator.
Postulate 2: Observables, Operators, and Eigenstates
• To every physically measurable quantity A, called an observable or dynamical
variable, there corresponds a linear Hermitian operator (Â ) whose eigenvectors form a
complete basis.
• The dynamical variables in physics are position, velocity, linear momentum, angular
momentum and energy.
• Suppose the quantum state Ψ𝑗 satisfies: ÂΨ𝑗 =𝑎𝑗 Ψ𝑗 (2)
• From equation (2), where  is an operator representing an observable, and 𝑎𝑗 is a
constant.
• Then Ψ𝑗 and 𝑎𝑗 are the jth eigenstate and eigenvalue of Â, respectively.
• If the system is in the state Ψ𝑗 , then the result of a measurement of the observable
represented by the operator  must be the eigenvalue (𝑎𝑗 ).
An operator (Â ) is a mathematical rule that when applied to wave functions (Ψ )
transforms it into another wave functions (Ψ′ ) of the same space eq.(4). Are non-
commutative dynamical variables. For any two operators A and B, AB ≠BA but
for any two c-number (not operators) observables C and D, CD = DC.
Â𝜳 = 𝜳′ (4).
 Examples of operators:
 Unity operator: it leaves any wave functions unchanged, Î Ψ= Ψ.
 The gradient operator:
𝜕𝜓 𝑟 𝜕𝜓 𝑟 𝜕𝜓 𝑟
𝛻𝜓 𝑟 = i+ j + 𝑘
𝜕𝑥 𝜕𝑦 𝜕𝑧
• The linear momentum operator: 𝑃𝜓 𝑟 = −𝑖ℏ𝛻𝜓 𝑟
• The Laplacian operator:
2 𝜕2 𝜓 𝑟 𝜕2 𝜓 𝑟 𝜕2 𝜓 𝑟
𝛻 𝜓 𝑟 = + +
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
• The parity operator: 𝑃𝜓 𝑟 = 𝜓 −𝑟
Postulate 3: Quantum Superpositions
• If a measurement of the observable corresponding to the operator  is made on
the normalized quantum state (Ψ), given by, Ψ = 𝑛 𝑐𝑛 Ψ𝑛 (3)
• where the Ψ𝑛 ’s are eigenstates of  and the 𝑐𝑛 ’s are expansion coefficients, then
𝑎𝑗 ( the eigenvalue of Ψ𝑗 ), will be obtained with probability |𝑐𝑗 |2 . Where,
|𝑐 | 2 = 𝑐 ∗ 𝑐 ∗ = 1 called normalization.
𝑛 𝑛 𝑛 𝑛
Schrödinger equation: We assume Ψ(x, t) may be written as the product of a
function T, which depends only on t, and another function ψ, which depends only
on x: Ψ(𝑥, 𝑡) = 𝑇(𝑡)𝜓(𝑥). Then Eq. (1) becomes:
𝑑𝑇 1 𝑑𝑇(𝑡) 1
𝑖ħ Ψ x = 𝑇 𝑡 Ĥ Ψ(x) & 𝑖ħ = ĤΨ(x) …… (4)
𝑑𝑡 𝑇(𝑡) 𝑑𝑡 Ψ(x)
• Here we have used the fact that dt does not alter ψ(x), and Ĥ does not alter T(t).
• Because the left-hand side of the (second) equation above now depends only on
t, and the right-hand side depends only on x, both sides must be equal to the
same constant. As such, we can write: ĤΨ(x) = E Ψ(x)………. (5), this equation
is the TISE.