University of Sialkot

Department of Chemistry, Faculty of Sciences

Physical Chemistry-II
CHEM-3001
Submitted by: Samra
Roll no: 18104008-006
“Review of Atkins’ Physical Chemistry and Essentials of Physical Chemistry by BS Bahl”
Submitted to: Miss Fozia Noreen
Course Instructor Physical Chemistry
Semester-V, Fall-2020
Batch 2018
Submission date: -12-2020
 Table of contents
1. Black body radiations------------------------------------------------------------------------------3
2. Wave particle duality------------------------------------------------------------------------------3-4
a) Particle character of Electromagnetic radiations
b) Wave character of Electromagnetic radiations
3. Compton Effect-------------------------------------------------------------------------------------4
4. Sommerfeld modifications of Bohr model------------------------------------------------------4-5
5. Heisenberg Uncertainty principle-----------------------------------------------------------------5
6. Schrodinger Wave equation-----------------------------------------------------------------------5-6

2
 Quantum Chemistry
Introduction:
Quantum chemistry focus on the applications of quantum mechanics to chemical systems. It was
thought that the motion of atoms and subatomic particles could be expressed using classical
mechanics, the laws of motion introduced in the seventeenth century by Newton, these laws were
very successful at explaining the motion of everyday objects and planets. However, towards the
end of the nineteenth century, experimental evidence show that classical mechanics failed when
it was applied to particles as small as electrons, and it took until the 1920s to discover the
concepts and equations for describing them. So, the concepts of quantum mechanics were
described.

Black Body Radiation:

All objects emit electromagnetic radiation over a range of frequencies with an intensity, depends
on temperature of object. A common example is a heated metal that first glows red and then
becomes ‘white hot’ upon further heating. The radiations emitted by hot objects is discussed in
terms of a black body. A good approximation to a black body is a small hole in an empty
container. The intensity of the radiation from a black body varies with wavelength at several
temperatures. At each temperature T there is a wavelength, λ max at which the intensity of the
radiation is a maximum, with T and λ max related by the empirical Wien’s law: λ max T= 2.9 ×10-3
m K. The explanation of black-body radiation was a major challenge. The physicist Lord
Rayleigh studied it theoretically from a classical viewpoint. He regarded the presence of
radiation of frequency ν (and therefore of wavelength λ = c/ν) as signifying that the
electromagnetic oscillator of that frequency had been excited. Rayleigh calculate the average
energy of each oscillator as k T. Then, with minor help from James Jeans, he arrived at the
8 πkT
Rayleigh–Jeans law, dE = ρdλ and ρ= 4
λ
Unfortunately Rayleigh’s law is successful at long wavelengths
(low frequencies), it fails at short wavelengths (high
frequencies). This mismatch became known as Ultraviolet
Catastrophe. .In 1900, Max Planck found that the experimentally
observed intensity distribution of black-body radiation could be
explained by proposing that the energy of each oscillator is
limited to discrete values. In particular, Planck assumed that for
an electromagnetic oscillator of frequency ν, the permitted
energy is E =h ν. The limitation of energies to discrete values is
called energy quantization. On this basis Planks was able to
derive an expression for energy spectral density, called the Figure 1
Planck distribution.
Wave-particle duality:

3
 Electromagnetic radiation which classical physics treats as wave-like actually also show the
characteristics of particles. Another experiment shows that electrons which classical physics
treats as particles, also display the characteristics of waves.
a) Particle character of electromagnetic radiation:
The Planck treatment of black-body radiation introduced the idea that an oscillator of frequency
ν can have only the energies 1hν, 2hν and so on. This quantization leads to suggestion that
particles of electromagnetic radiation are now called photons. The existence of photons is only a
suggestion till the experimental evidence for their existence comes from the measurement of the
energies of electrons produced in the photoelectric effect, which is a process of ejection of
electrons from metals when they are exposed to ultraviolet radiation. Observations of the
photoelectric effect strongly suggest that a particle-like projectile collides with the metal and, if
the kinetic energy of the projectile is high enough, an electron is ejected. , the conservation of
energy implies that hν = K.E + Φ or K.E = hν – Φ.
b) Wave character of electromagnetic radiation:
The concept that radiations consist of particles were discarded until Davisson and Germer, who
observed the diffraction of electrons by a crystal. The Davisson and Germer experiment, which
has been repeated with other particles (including α particles, molecular hydrogen, and neutrons),
shows clearly that particles have wave-like properties. At almost the same time, G.P. Thomson
showed that a beam of electrons was diffracted when passed through a thin gold foil.
Some progress for wave-particle duality had already been made by Louis de Broglie who, in
1924, suggested that any particle, not only photons, travelling with a linear momentum p = mv
should have in some sense a wavelength given by what is now called the de Broglie relation: λ =
h
p

Compton Effect:
In 1923 A.H. Compton provided one more proof to the
quantum theory and presented Compton Effect, stated as
“ When X-rays of wavelength λ' struck a sample of
graphite, an electron was ejected and the X-rays
scattered at an angle θ had longer wavelength λ”. Thus
he argued that light radiation (X-rays) consisted of
particles (photons), as a continuous wave could not have
knocked out the electron. He visualized that a photon of
incident light struck a stationary electron in graphite. Figure 2
Hence lost some energy which resulted in the increase of wavelength. This process could not
have occurred unless light radiation consisted of particles or photons. By assuming photon-
electron collisions to be perfectly elastic, Compton found that the shift in wavelength, dλ was
2h 2 θ
given by the expression, dλ = sin .So h is Planck’s constant, m the mass of an electron, c
mc 2

4
the velocity of light and θ the angle of scattering. The expression shows that dλ is independent of
the nature of the substance and wavelength of the incident radiation.

Sommerfeld modifications of Bohr Atomic Model:

When spectra were examined with spectrometers, each line was found to consist of several
closely packed lines. The existence of these multiple spectral lines could not be explained on the
basis of Bohr’s theory. Sommerfeld modified Bohr’s theory as follows. Bohr considered electron
orbits as circular but Sommerfeld postulated the presence of elliptic orbits also. An ellipse has a
major and minor axis. A circle is a special case of an ellipse with equal major and minor axis.
The angular momentum of an electron moving in an elliptic orbit is also supposed to be
quantized. Thus only a definite set of values is permissible. It is further assumed that the angular
momentum can be an integral part of h/2π units, where h is Planck’s constant. Or that,
kh
Angular momentum =
2π
Where k is called the azimuthal quantum number, whereas the quantum number used in Bohr’s
theory is called the principal quantum number. The two quantum numbers n and k are related by
the expression:
n length of major axis
=
k length of minor axis

Heisenberg Uncertainty Principle:

One of the most important consequences of the dual nature of matter is the uncertainty principle
developed by Werner Heisenberg in 1927. This principle is an important feature of wave
mechanics and discusses the relationship between a pair of conjugate properties (those properties
that are independent) of a substance. According to the uncertainty principle, it is impossible to
know simultaneously both the conjugate properties accurately. For example, the position and
momentum of a moving particle are interdependent and thus conjugate properties also. Both the
position and the momentum of the particle at any instant cannot be determined with absolute
exactness or certainty. If the momentum (or velocity) be measured very accurately, a
measurement of the position of the particle correspondingly becomes less precise. On the other
hand if position is determined with accuracy or precision, the momentum becomes less
accurately known or uncertain. Thus certainty of determination of one property introduces
uncertainty of determination of the other. The uncertainty in measurement of position, Δx, and
the uncertainty of determination of momentum, Δp are related by Heisenberg’s relationship as
h
Δx×Δp≥
2π
h
Δ x × m Δv ≥
2π

5
There exists a clear difference between the behavior of large objects like a stone and small
particles such as electrons. The uncertainty product is negligible in case of large objects.

Schrodinger Wave Equation:

In classical mechanics an object travels along a definite path or trajectory. In quantum mechanics
a particle in a particular state is described by a wave function, ψ (psi), which is spread out in
space, rather than being localized. The wave function contains all the dynamical information
about the object in that state, such as its position and momentum.
In 1926, the Austrian physicist Erwin Schrodinger proposed an equation for finding the wave
function of any system. His equation is the keynote of wave mechanics and is based upon the
idea of the electron as ‘standing wave’ around the nucleus. The Schrodinger equation is a
second-order differential equation used to calculate the wave function of a system. It has several
solutions. Some of these are imaginary and are not valid. If the potential energy term is known,
the total energy E and the corresponding wave function ψ can be evaluated. A wave function is
normalized if the integral over all space of its square modulus is equal to 1. A wave function
must be single-valued, continuous, and not infinite over a finite region of space, and (except in
special cases) have a continuous slope. The Schrodinger equation can be written in the succinct
form Ĥ ψ = E ψ. The operator Hˆ plays a special role in quantum mechanics, and is called the
Hamiltonian operator after the nineteenth century mathematician William Hamilton, who
developed a form of classical mechanics which, it subsequently turned out, is well suited to the
formulation of quantum mechanics. The Hamiltonian operator is the operator corresponding to
the total energy of the system, the sum of the kinetic and potential energies. When Hamiltonian
operator acts on wave function and regenerate the same wave function along its constant value, is
called Eigen function and thus, (operator)(function) = (constant factor) × (same function). If a
general operator is denoted Ωˆ (where Ω is uppercase omega) and the constant factor by ω
(lowercase omega), then an eigenvalue equation has the form Ωψ = ω ψ.
According to the theory of propagation of light and sound waves, the square of the amplitude of
the wave is proportional to the intensity of the sound or light. A similar concept, modified to
meet the requirement of uncertainty principle, has been developed for the physical interpretation
of wave function ψ. This may be stated as the probability of finding an electron in an extremely
small volume around a point. It is proportional to the square of the function Ψ 2 at that point. If
wave function ψ is imaginary, ψψ* becomes a real quantity where ψ* is a complex conjugate of
ψ. This quantity represents the probabilityΨ 2 as a function of x, y and z coordinates of the
system, and it varies from one space region to another. Thus the probability of finding the
electron in different regions is different.

Conclusion:
So we reviews some of the basic principles of quantum mechanics. First, the experimental results
that overthrew the concepts of classical physics. These experiments led to the conclusion that
particles may not have an arbitrary energy and that the classical concepts of ‘particle’ and ‘wave’
blend together. The overthrow of classical mechanics inspired the formulation of a new set of

6
concepts and led to the formulation of quantum mechanics. In quantum mechanics, all the
properties of a system are expressed in terms of a wave function that is obtained by solving the
Schrodinger equation. We see how to interpret wave functions. Finally, we analyze some of the
techniques of quantum mechanics in terms of operators, and see that they lead to the uncertainty
principle, one of the most profound departures from classical mechanics.