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INTRODUCTION - ORIGINS OF THE

QUANTUM THEORY

G. Birungi 1

• Quantum chemistry course Outline

– Fundamental principles of quantum
mechanics
– Applications to simple systems
– Atomic structure
– Molecular structure and Chemical bond

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Quantum Theory
• The term “Quantum Mechanics” was first coined
by Max Born in 1924

• Quantum Mechanics is made up of two words

QUANTUM + MECHANICS.
– “Mechanics” refers to the science of motion of the
body. We are dealing with motion of the particle.
– “Quantum” which is Latin word for amount and in
modern conventions is used to represent smallest
possible discrete unit of any physical property.

• The term Quantum came into use during 1900 by So…What is

physicist Max Planck who wrote a mathematical quantum
equation involving a figure to represent individual mechanics?
units of energy. He called the units Quanta (plural
of Quantum).

Quantum Theory
• Quantum mechanics is the science of
motion of micro particles i.e.
atomic and subatomic particles

• Quantum Mechanics is a theoretical

science of microscopic matter
(electrons and nuclei in atoms and
molecules).
So…What is
the role of
• It gives the laws of motion of quantum
microscopic objects (the way mechanics in
classical mechanics gives for Chemistry?

macroscopic objects).
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Role of Quantum Mechanics

In Chemistry…
• Quantum chemistry explains theoretically structure,
bonding and reactivity (SBR) in chemical entities
taking into account the role and behavior of electrons

• The influence of quantum chemistry is evident in all

branches of chemistry.

– Organic chemistry utilizes quantum mechanics to estimate

the relative stabilities of molecules, to calculate properties
of reaction intermediates, to investigate the mechanisms of
chemical reactions, and to analyze NMR spectra.

– Analytical chemistry uses spectroscopic methods

extensively which stem from fundamentals of quantum
chemistry. All the spectra are understood and interpreted
via thorough understanding of the basics of quantum
mechanics.
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In Chemistry…
– Inorganic chemistry utilizes ligand field theory which
is an approximate quantum mechanical method used
to predict and explain the properties of transition-
metal complex ions. Entire atomic structure comes
from Quantum Mechanics – orbitals, shape of orbitals,
bonding etc.

– Physical chemistry applies the results of quantum

mechanics to calculate thermodynamic properties,
molecular properties etc. for bulk matter via statistical
mechanics.
𝑠𝑡𝑎𝑡𝑖𝑠𝑡𝑖𝑐𝑎𝑙 𝑚𝑒𝑐ℎ𝑎𝑛𝑖𝑐𝑠
• 𝑄𝑢𝑎𝑛𝑡𝑢𝑚 𝑚𝑒𝑐𝑕𝑎𝑛𝑖𝑐𝑠 → 𝑆𝑖𝑛𝑔𝑙𝑒 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝐵𝑢𝑙𝑘 𝑏𝑒𝑕𝑎𝑣𝑖𝑜𝑢𝑟

• Biochemistry where quantum mechanical studies on biological

molecules, enzyme substrate binding etc., have been carried out
successfully
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Quantum Theory
• Understanding quantum theory is important
because it helps to explain :
– Properties of atoms and molecules (e.g.
physicochemical properties, their structure, spectral
behavior, reactions) can be interpreted in terms of the
motions of micro particles e.g. electrons and protons.
• The dynamic properties of a particle (e.g. position,
momentum, energy) are determined by the laws of
mechanics
• Classical mechanics also does not put any restrictions on the
values of the dynamic properties of a particle
– However:
• Experimental measurement of atomic
and molecular systems shows that This can not be
an electron moving around the nucleus explained by classical
of an atom has only discrete set of values mechanics
of energy
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Origin of Quantum Theory

• Quantum theory arose from the need to explain discreteness
(quantization)
• The origin of quantum theory can be marked by the
phenomena below involving electromagnetic radiation, which
could not be adequately explained by the methods of
classical physics (determinism):
• Blackbody radiation - Max Planck in 1900.
• The photoelectric effect - Albert Einstein in 1905.
• The origin of line spectra -Neils Bohr in 1913.
• Compton effect
• Heat capacity of solids

• A clear formulation of quantum mechanics was developed in

1925 and 1926, through the work of Schrödinger, Heisenberg
and Dirac.

Side Note: Classical mechanics gives laws of motion of macroscopic objects whereas
Quantum mechanics gives laws of motion of microscopic objects 9

Radiation
• Radiation is defined as a wave that consists of
oscillating electric (E) and magnetic fields (B); hence
it is also called electromagnetic wave

• Photon - A unit of electromagnetic radiation e.g.

light

– Electromagnetic waves - First demonstrated

experimentally by Heinrich Hertz in 1887 (By
production and detection of the electromagnetic
waves predicted by Maxwell (radio waves)by
acceleration of electrical charges) 10

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Radiation
• Radiation is characterized by its wavelength () and frequency ()
– The wavelength, , is the distance between successive maxima
of the electric (or magnetic) field.

– The frequency, , represents the number of oscillations per

second observed at a fixed point in space.

– The reciprocal of frequency, 1/, represents period of oscillation

(the time it takes for one wavelength to pass a fixed point)

– The speed of propagation of the wave is therefore determined by

 = C (C= 3×108 ms-1)

• Different solids emit radiation at different rates at the

same temp; the rate is maximum when the solid is
perfectly black (black body)
– A black body can absorb all radiation that falls on it

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Black Body Radiation

• A Black Body is an idealized physical body that
absorbs and emits radiations of all frequencies of
radiation uniformly

• A good approximation of a black body is a pinhole

container maintained at a uniform temperature

• A graph of observed spectral output of a black body

(power emitted as a function of wavelength) has a
characteristic shape in which the power increases
through a maximum as the wavelength decreases

• At higher temperature T, the wavelength of the

peak emission shifts to shorter wave length and
the total power emitted (area under the curve)
increases proportionally as T4. 12

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Distribution of Energy in Black Body Radiation

• Experimentally it is
found that:
– At any temperature T,
the energy density 
() increases with ,
reaches a maximum
and then falls off to
zero.

– As T increases the
point of maximum
shifts to higher
frequency (shorter
Fig.1 Intensity as a function of wavelength
wave length) side 13

Blackbody Radiation
• Why would some metals be “red” hot; “white” hot
or “blue” hot as you increase temp?

– Embers of coal in a fire glow red while a hotter object

like the sun appears yellow-white because of the
greater contribution from shorter wave length
blue light to the visible part of the emission

• Is radiation released in a continuum?

• If UV and higher frequencies were produced in an

increasing number, what would be the temp of the
earth?
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Blackbody Radiation

• In order to derive a formula to account for

the shape of the curves in fig.1, Rayleigh
and Jeans assumed that:
– The oscillators which comprise
electromagnetic radiation could oscillate
at any frequency and therefore all
wavelengths, , of radiation were possible
8𝜋𝑘𝑇
The resulting equation is  + 𝑑 = 𝑑
4

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Blackbody Radiation

The equation describes the intensity of

blackbody radiation as a function of
wavelength, λ (or frequency, ν) for a fixed
temperature is known as the Rayleigh-Jeans
law also written as:

8𝜋𝑘𝑇
𝜌 , 𝑇 =
4
• Where k is Boltzman constant (1.381 × 10-23𝐽𝐾-1)
• 𝜌 𝑟𝑒𝑓𝑒𝑟𝑠 𝑡𝑜 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑡𝑎𝑡e𝑠, 𝜆 𝑖𝑠 𝑡𝑕𝑒 𝑤𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡𝑕
𝑎𝑛𝑑 𝑇 𝑖𝑠 𝑡𝑕𝑒 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
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Distribution of Energy in Black Body Radiation

• Radiation emitted by a black body is not confined

to a single wavelength; rather it is spread over a
wide spectrum of wavelengths
• Distribution of radiant energy over the different
frequencies is described in terms of a function 
() d which denotes the amount of radiation in
the frequency range  + d
• Lord Rayleigh (1900) attempted to describe
blackbody radiation using classical laws of
mechanics
– He derived the equation 𝝆 𝝂 𝒅𝝂 = 𝑨𝝂𝟐 𝑻
– Thus a plot of 𝝆 𝝂 against  runs to infinity as 
increases without showing any maximum

• Experimental measurements showed otherwise! 17

Black Body Radiation

• Although Rayleigh-
Jeans law works for
higher wavelengths it
fails to correctly
reproduce
experimental trends at
shorter wavelengths;

• This divergence for low

wavelengths is called the
Ultraviolet Catastrophe

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Black Body Radiation

• Max Planck in 1900 proposed that:

– Energies involved in absorption and emission

of electromagnetic radiation did not belong
to a continuum (as implied by Maxwell's
theory)

• Energies involved were made up of discrete

bundles called “quanta”

• A quantum associated with radiation of

frequency  has the energy E = h
• h = 6.626  10 -34 J sec and is known as Planck's constant.

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Black Body Radiation

• Planck was able to derive this formula by
assuming that the energies of the oscillations
of electrons which gave rise to the radiation
were proportional to integral multiples of the
frequency, i.e.,
– 𝑬 = 𝒏𝒉𝝂, 𝒏 = 𝟎, 𝟏, 𝟐………
– where  is the frequency of radiation and h is
Planck’s constant.

• This limitation of energy to discrete values is

called the quantization of energy.
– This was the first use of notion of quantization of
energy.

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Black Body Radiation

• On 14th December 1900, Max Planck at the
meeting of German Physical Society proposed an
equation similar to the Rayleigh-Jeans equation to
explain black- body radiation with an adjustable
parameter h.
8𝜋𝒉𝐶
• 𝜌 , 𝑇 = OR
5 (𝑒 𝒉𝒄 𝑘𝑇)−1)

8𝜋ℎ𝐶 1
•  + 𝑑 = 𝑑
 4 ℎ𝑐
𝑒 𝑘𝐵 𝑇 −1

– Planck found that for h = 6.626 x 10-34 J s, the

experimental data could be reproduced.
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Quantization
• Quantization refers to a situation where physical
quantities, like position, energy and momentum
can have only certain discrete values.

• Quantization Concept: Bohr’s model was the first

model to give the quantization concept by the
𝑛ℎ
equation: 𝑚𝑣𝑟 = 𝑛 = 1,2,3……
2𝜋
– Where m is the mass of electron, v is the linear velocity of
electron, r is the radius of the orbit and n is an integer.
– Bohr postulated that the angular momentum of an
electron can have only discrete values given by above
equation.
– However, the above equation was given without any proof
and there was no reason to explain quantization.
– Therefore, quantization was not taken seriously at that
time.
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Quantization
• Radiation consists of discrete packets of energy
called Quanta. It is the basic unit (“quantum”) of
electromagnetic radiation.

• Why was this phenomenon misinterpreted by

classical mechanics?
– This is because classical mechanics considered an
electromagnetic radiation solely wave phenomena.

• However, Planck proposed that radiant energy (or

radiation) is made up particle like components
known as “quantum” along with wave picture of
radiation.
– Planck proposed that energy can be transferred only
in discrete amounts. 23

The Photoelectric Effect

• When visible or ultraviolet radiation impinges on clean
metal surfaces, it can cause electrons to be ejected
from the metal.
• The ejection of electrons from the surface of a metal
by radiation is called Photoelectric effect.

– Such an effect is not, in itself, inconsistent with classical

theory since electromagnetic waves are known to carry
energy and momentum.

– But the detailed behavior as a function of radiation

frequency and intensity can not be explained classically. 24

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The Photoelectric Effect

• The energy required to eject an electron
from a metal is determined by its work
function . For example, sodium has  =
1.82 eV.
– 1 eV = 1.60210-19J.

– The classical expectation would be that

radiation of sufficient intensity should cause
ejection of electrons from a metal surface,
with their kinetic energies increasing with the
radiation intensity.
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The Photoelectric Effect

• The experimental facts are quite different:
– It is found that no electrons are ejected, no
matter how high the radiation intensity, unless
the radiation frequency exceeds some
thresh hold value 0 for each metal (varies
from metal to metal) i.e. a minimum energy
must be attained E = h0 for an electron to be
ejected (to satisfy the work function )

– Kinetic energy of the emitted electrons

increases on increasing the frequency but
remains unaffected on increasing the intensity
of the light
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The Photoelectric Effect

• Einstein accepted Planck's hypothesis that :
– A quantum of radiation carries an energy h.
– Thus, if an electron is bound in a metal with an
energy , a quantum of energy h0 =  will be
sufficient to dislodge it.
– And any excess energy h( -0) will appear as
kinetic energy of the ejected electron.

• Einstein believed that the radiation field

consist of quantized particles, which he
named photons
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The Photoelectric Effect

• When a light photon of a particular frequency () hits
an electron in a metal, it transfers its energy h to the
electron.

• The electron uses this quantum energy to overcome

the energy () that binds it in the metal and to
1
increase its own kinetic energy (2 𝑚𝑣 2 )
𝟏
i.e 𝒉𝝂 = 𝝎 + 𝒎𝒗𝟐
𝟐

• If h < , the photon will not have sufficient energy to

eject the electron from the metal surface (no
photoelectric effect)

• As the frequency,, increases, the kinetic energy of the

electrons also increases
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Compton Effect
• Compton Effect refers to the shift in the wavelength
upon scattering of light from stationary electrons.

• It was observed that when monochromatic X-rays of a

known wavelength interacted with atoms, the X-rays
scattered through an angle  and emerged at a
different wavelength related to  .

• The scattered photon X-rays have wavelengths larger

than the incident rays.
– This means photons become less energetic on scattering.

• This could not be explained by wave nature of

radiation alone.

• Compton explained the X-ray shift by attributing

particle-like momentum to photons. 29

Compton Effect
• Compton derived a mathematical relationship
between the shift in wavelength and the scattering
angle of the X-rays by assuming that each scattered X-
ray photon interacted with only one electron

ℎ
∆ = 𝑠 − 𝑖 = 𝑚 (1 − 𝑐𝑜𝑠)
𝑒𝐶
– where
– Δ𝜆 𝑖𝑠 𝐶𝑜𝑚𝑝𝑡𝑜𝑛 𝑠𝑕𝑖𝑓𝑡
– i is the initial wavelength,
– s is the wavelength after scattering,
– h is the Planck constant,
– meis the Electron rest mass,
– C is the speed of light, and
–  is the scattering angle.

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Compton Effect
• According to the equation, the Compton shift should be
independent of the wavelength of the incident X-rays.

• This has been found to be so experimentally.

– The shift in wavelength is independent of initial wavelength and
also of the nature of the element.
– It depends only on the angle of scattering.

– 𝐼𝑓 𝜃 = 0° Δ𝜆 = 0 𝑁𝑜 𝑤𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡𝑕 𝑠𝑕𝑖𝑓𝑡
– 𝐼𝑓 𝜃 = 90° Δ𝜆 = 2.42𝑝𝑚 𝑆𝑐𝑎𝑡𝑡𝑒𝑟𝑒𝑑 𝑟𝑎𝑑𝑖𝑎𝑡𝑖𝑜𝑛 𝑝𝑒𝑟𝑝𝑒𝑛𝑑𝑖𝑐𝑢𝑙𝑎𝑟 𝑡𝑜 𝑖𝑛
𝑐𝑖𝑑𝑒𝑛𝑡 𝑟𝑎𝑑𝑖𝑎𝑡𝑖𝑜𝑛
– 𝐼𝑓 𝜃 = 180° Δ𝜆 = 𝑇𝑤𝑖𝑐𝑒 𝐶𝑜𝑚𝑝𝑡𝑜𝑛 𝑤𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡𝑕

• The success of using energy and momentum conservation to

explain the experimental data for the Compton Effect is
powerful evidence that electromagnetic radiation has
momentum just like a particle. This supports the Einstein
“photon” concept
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Line Spectra
• A continuous spectrum can be produced by an
incandescent solid or gas at high pressure

• An absorption spectrum results when light from a

continuous source passes through a cooler gas,
consisting of a series of dark lines characteristic of the
composition of the gas

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Line spectra cont…

• Line spectra are characteristic of the atomic composition of
the gaseous element

• It is consistent with classical electromagnetic theory that

motions of electrical charges within atoms can be associated
with the absorption and emission of radiation.
– But how does such radiation occur for discrete frequencies,
rather than as a continuum?
33

Atomic Spectra
• The spectrum of light emitted by energetic atoms is
composed of individual lines of different colors.

• These lines represent the discrete energy levels of the

electrons in those excited atoms.

• When an electron in a high energy state jumps down to a

lower one, the atom emits a photon of light which
corresponds to the exact energy difference of those two levels
(conservation of energy).

• If electrons were not restricted to discrete energy levels, the

spectrum from an excited atom would be a continuous spread
of colors from red to violet with no individual lines.

• This again indicates that energy is quantized.

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Atomic Spectra
• Building on the ideas of Planck
and Einstein, Bohr postulated
that:

– The energy levels of atoms belong

to a discrete set of values En,
rather than a continuum.

– When an atom makes a

downward energy transition from
a higher energy level Em to a
lower energy level En, it causes the
emission of a photon of energy
• E = h = Em – En

• This is what accounts for the

discrete values of frequency 
in emission spectra of atoms
35

Atomic Spectra
• In 1913, Niels Bohr derived the discrete lines of the
hydrogen spectrum with a simple atomic model in
which the electron circles the proton just as a
planet orbits circle the sun

– Central to his model are two postulates

1. In the absence of radiation absorption or emission,

electrons stay in a stationary state.

2. Absorption occurs only in discrete amounts,

corresponding to a change in energy between two
stationary states of the electron.
ΔE = hν then gives the frequency of the radiation.

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Rydberg Equation
• Rydberg (1890) found that all the lines of the atomic hydrogen
spectrum could be fitted to a simple empirical formula

1 1 1
– =𝑅 − , 𝑛1 = 1,2,3. . , 𝑛2 > 𝑛1
𝜆 𝑛1 2 𝑛2 2
• R, is the Rydberg constant, =109,677 cm-1.

• This formula was found to be valid for hydrogen spectral lines in the
infrared and ultraviolet regions, in addition to the four lines in the
visible region

• Bohr proposed a model for the energy levels of a hydrogen atom

which agreed with Rydberg's formula for radiative transition
frequencies.

• Inspired by Rutherford's nuclear atom, Bohr suggested a planetary

model for the hydrogen atom in which the electron goes around the
proton in one of a set of allowed circular orbits

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Bohr’s Model of the Atom

Stylized Representation of the
Planetary Model of the Atom
model for a multi-electron atom

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Heat Capacity of Solids

• In the early 19th century, two French scientists Dulong and Petit
determined the heat capacities 𝐶 = (𝜕𝑈/ 𝜕𝑇), of a number of
monoatomic solids.

• They proposed that molar heat capacities of all mono-atomic solids

are the same, independent of temperature and close to25 JK-1mol-1

• From classical mechanics, the equipartition principle could be used to

infer that the mean energy of an atom as it oscillates about its mean
position in a solid is kT for each of displacement.

• In three dimensional space the average energy of each atom is 3kT.

• For N atoms, the total energy becomes 3NkT. With this, the molar
internal energy becomes 𝑈m = 3𝑁A𝑘𝑇 = 3𝑅𝑇. 𝑅 = 𝑁a𝑘 = 𝑔𝑎𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
• 𝐶m = (𝜕𝑈m/ 𝜕𝑇) = 3𝑅 ≈ 25𝐽𝐾-1𝑚𝑜𝑙-1

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Heat Capacity of Solids

• However, it was experimentally found that molar heat
capacities are not independent of temperature.

• It was found that the molar heat capacities of all

mono-atomic solids are lower than 3R at low
temperatures and that the values approaches zero as 𝑇
→ 0.
• Einstein (in 1905) assumed that each atom oscillated
about its position with a frequency  and invoked
Planck’s hypothesis to assert that the energy of
oscillation is confined to discrete values, following the
Planck’s equation,
– 𝑬 = 𝒏𝒉𝝂, 𝒏 = 𝟎, 𝟏, 𝟐………
• Einstein calculated the total molar internal energy of
the solid and obtained the following expression:
41

Heat Capacity of Solids

• 𝐶m = 3𝑅𝑓 𝑣𝑎𝑟𝑖𝑒𝑠 𝑓𝑟𝑜𝑚 0 𝑡𝑜 3𝑅
 𝑒  𝑇
– 𝑓 = ( 𝑇 )2 2 = 𝑓(𝑇)
𝑒  𝑇 −1
– 𝜃 = 𝑕𝜈/ 𝑘 (𝐸𝑖𝑛𝑠𝑡𝑒𝑖𝑛 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒)

• Einstein temperature expresses the frequency

of oscillation of the atoms as a function of
temperature

• Einstein explained dependence of heat

capacity of solids assuming quantization of
energy.
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Waves and Particles

• Certain phenomena of light e.g. diffraction,
interference could be explained only in terms of wave
concept while photoelectric effect could be explained
in terms of particle (photon) concept
• This confusion was solved by a proposition that
electromagnetic radiation has a dual character, particle
and wave

• The duality is inherent in the Planck’s equation E= h

• Einstein in his theory of relativity pointed out that a
photon travelling with the speed of light has a mass
(m) and that its energy is E = mC2
• Thus h = mC2

43

The Dual Nature of Light

• Planck equation • Reorganizing this
equation gives:

• Einstein's equation

– Thus the wavelength of a

• Combining Planck and photon is inversely
Einstein's equation for a related to the momentum
proton of mass m p via Planck's constant

Light has both particle and wave properties44

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The Dual Nature of Light

• Louis de Broglie suggested that not only

light has particle characteristics, but that
classical particles, such as electrons, have
wave characteristics
• Recall: The wavelength  of these waves and
particle momentum p are related through p =
h/.

• Erwin Schrödinger was intrigued by de

Broglie’s ideas and set his mind on finding
a wave equation for the electron
45

Matter Waves
• Quantization is inherent in wave motion
– E.g. a string fixed at the two ends can vibrate at
frequencies , 2, 3 etc, its frequencies are
quantized and a vibration is the same as a wave
motion
• According to Louis de Broglie,
– Quantization of energy in an atom can be
explained if electronic motion is considered as a
wave motion
• The wavelength or frequency of the electron can
thus be calculated by analogy with that of photons
ℎ
i.e 𝜆 = 𝑃
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Matter Waves

• The wave length of a material particle likewise

can be given by
𝑕
𝜆=
𝑚v
– Where m is mass, v is velocity of the particle, h
is Planck's constant
• Notes
– For smaller particles e.g. electrons, the magnitude of
wavelength will show that the wave effects can be felt
(bigger than h)
– For larger particles however the wavelength will be
too small (close to the value of h) to lead to
observable wave effects 47

Heisenberg Uncertainty Principle

• “It is not possible to determine both the position

and the momentum of an electron with equal
accuracy”
– The more exactly we determine the position the less
exact the momentum becomes and vice-versa
• Δ𝑥 × Δ𝑝𝑥  𝑕

• The uncertainty explains the inadequacy of the

Bohr theory of well defined orbits
• Example
– Consider an electron (mass = 9.109 × 10 -31 Kg)
moving in a hydrogen atom in the first orbit with a
speed of 2× 10 6 M/s.
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Heisenberg Uncertainty Principle

• The momentum will be mv = 9.109 × 10−31 × 2 ×
106 = 18.218 × 10−25 𝐾𝑔𝑚𝑠 −1
• If this is measured with accuracy of 1%, the uncertainty
of the momentum will be 18.218 × 10−25 𝐾𝑔𝑚𝑠 −1 ×
1% = 18.218 × 10−27 𝐾𝑔𝑚𝑠 −1
• The uncertainty of the position will be
ℎ 6.625 ×10−34 𝐽𝑠
– Δ𝑥 = ∆𝑝
= 18.218 ×10−27 𝐾𝑔𝑚𝑠−1 = 3.64 × 10−8 𝑚

• The radius of the first orbit in a H-atom = 0.0529 nm

– The uncertainty of the electron’s position would thus be =
36/0.0529  700 !

49

Plank’s Quantum Theory- Summary

 Based on the concept of the • Quantum mechanics was

quantum unit to describe the motivated by two experimental
dynamic properties of subatomic observations:
particles and the interactions of – The quantization of energy
matter and radiation. transfer in light-matter
• Max Planck, in 1900 postulated interactions
that energy can be emitted or – The dual wave-particle
absorbed by matter only in nature of both light and
small, discrete units called matter
quanta. • Max Planck calculated the
• Fundamental to the development spectrum of black-body radiation
of quantum mechanics was the by postulating that
Heisenberg uncertainty principle, – “an electromagnetic field can
which states that “the position exchange energy with atoms
and momentum of a subatomic only in quanta”
particle cannot be specified • E = h
simultaneously
50

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Quantization of Energy, Particle Wave-Duality- Key notes –

The failures of classical physics
Quantization
The Planck constant
The ultraviolet catastrophe
Photoelectric effect
De Broglie equation

51

The Wave Nature of Matter

• Wave functions and Probabilities
– In the particle-wave duality interpretation of matter
and radiation, a particle moving in space can also be
described as a wave in space

– The wavelength is related to the particle momentum

ℎ
by De Broglie’s equation  = 𝑝

– In quantum mechanics, the concept of a particle

moving in defined trajectories in a system is replaced
by its wave function 

– The wave function  describes all the regions of

space in which the particle it represents can be
found
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The Wave Nature of Matter

– This introduces the idea of uncertainty
because the exact position of the particle at
point in time is not defined (only the region of
space of all its possible positions can be
defined)

– The exact shape of the wave function is

important because the probability of finding
the particle at each point is proportional to
2 at that point
• A greater amplitude in the wave function
corresponds to a greater probability density in the
particle’s distribution
53

Schrödinger Equation

• “When the Hamiltonian operator acts on a certain wave

function , and the result is proportional to the same wave
function  then  is a stationary state and the proportionality
constant, E, is the energy of the state 

– Each allowed wave function 1, 2, 3….. Of a system described by a

Hamiltonian operator H is associated with one particular allowed
energy level E1, E2, E3…

– The Hamiltonian is the operator corresponding to the

total energy of the system
– H is associated with one particular allowed energy level E1,
E2, E3….
• (An operator is a mathematical function that represents the
action of a physical observable)
54

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Schrödinger Equation
• The Hamiltonian operator is the operator for the total
kinetic and potential energy of the system

• Only an allowed wave function of the system,, when

operated on by H, returns the same wave function,
multiplied by the associated constant value E

• In mathematical terminology the Schrodinger

equation is an eigenvalue equation; the pairs of E
and  that satisfy the equation are eigenvalues and
eigenfunctions of H respectively

• A Schrödinger equation can be written to describe any

particular physical system

55

Schrödinger Equation
• For a particle of mass m moving in one dimension only (along
x- axis) the equation is:
ℏ2 𝑑2 
− + 𝑉 𝑥  = 𝐸
2𝑚 𝑑𝑥 2
ℏ2 𝑑2
– Where and 𝑉 𝑥 are operators for (one-dimensional)
2𝑚 𝑑𝑥 2
kinetic and potential energy respectively which constitute the
Hamiltonian operator
– ℏ represents h/2
• The Schrodinger equation can be shown to be consistent with
experimental observation by considering the equation for a
freely-moving particle that possesses kinetic energy only
ℏ2 𝑑 2 
• − 2𝑚 𝑑𝑥 2 = 𝐸
𝑑2  2𝑚𝐸
• Rearranging gives 𝑑𝑥 2 = − ℏ2 
2𝑚𝐸
• A solution to this equation is:  = 𝑠𝑖𝑛 ℏ2
x
56

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Schrödinger Equation
• This can be verified by differentiating the function twice
𝑑 2𝑚𝐸 2𝑚𝐸
= 𝐶𝑜𝑠
𝑑𝑥 ℏ2 ℏ2

𝑑2  2𝑚𝐸 2𝑚𝐸 2𝑚𝐸

𝑑𝑥 2
=− ℏ2
𝑠𝑖𝑛 ℏ2
𝑥 =− ℏ2


• The wavelength, , of a sine wave of form sin (kx) is

2
=
𝑘

• So the wavelength of the wave function associated with the

freely moving particle is:
ℏ2
 = 2
2𝑚𝐸 57

Schrödinger Equation
• Substituting using the relationship between kinetic
energy E and momentum p:
1 (𝑚𝑣)2 (𝑝)2
𝐸 = 𝑚𝑣 2 = =
2 2𝑚 2𝑚

• Remember ℏ = 𝑕 2𝑚 𝑡𝑕𝑢𝑠
𝑕2 2𝑚 𝑕
 = 2 2 2
=
4 2𝑚 𝑝 𝑝

• The final result is the De Broglie’s equation, i.e. the

Schrodinger equation reproduces the experimental
observation that a freely moving particle can be
described as a sine wave inversely proportional to the
particle momentum
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The Schrödinger Hamiltonian

• By analogy with classical mechanics, the Hamiltonian is
commonly expressed as the sum of operators corresponding
to the kinetic and potential energies of a system in the form

– H* = T*+V*

– V* = V = V(r,t) is the potential energy operator

– T* is the kinetic energy operator

• m is the mass of the particle

– is the momentum operator

–  is the gradient operator

59

The Schrödinger Hamiltonian

• In Three dimensions using Cartesian coordinates the Laplace
operator is

• Combining these together yields the familiar form used in the

Schrödinger equation
– H* = T*+V*

• This allows one to apply the Hamiltonian to systems described by a

wave function Ψ(r, t). This is the approach commonly taken in
introductory treatments of quantum mechanics, using the formalism of
Schrödinger's wave mechanics
60

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Schrödinger Equation
• Partial differential equation which describes how the quantum
state of a physical system changes with time.

• Describes wave function of a system also called quantum state

or state vector

• Time dependent Schrödinger Equation

• Where:
– i is imaginary unit
– h is the reduced planck’s constant (h/2)
– d/dt partial derivative with respect to time t
–  wave function of the quantum system
– H- Hamiltonian operator (Characterizes total energy of any given
wave functions and takes different forms depending on
situation)

61

The Schrödinger wave equation

• Erwin Schrödinger, applied the idea of the wave-
like property of electrons to the electronic
structure of the atom.

• Schrödinger equation
– H is the Hamiltonian operator
–  represents the wave function that describes the
system
– E is the energy of the system

• General form of Schrödinger equation

– A is an operator and c an observable (energy, E, in the
Schrödinger equation).
• An operator is a mathematical operation, e.g. differentiation,
multiplication with a factor, which is applied to a function
• functions Ψ is an eigen function of the operator 62

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The Schrödinger wave equation

• Differential equations of this type are of a special type
where there are a set of solutions (eigenvectors)
characterized by a set of eigen values En.

• The situation in a simple atom, such as hydrogen, is

more complicated.

– The electron is in motion around a central nucleus in

three-dimensional space.

– This is often called the central force field situation

– When a wave equation is written for this situation, it is

called the Schrödinger wave equation for the atom.
63

The Schrödinger wave equation

– As written below, it applies to the hydrogen

atom if the appropriate form of V is supplied.

– This form of the equation is known as the time-

independent Schrödinger equation.

– It is a special case of the more general time-

dependent Schrödinger equation.

64

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The Schrödinger wave equation

– Solutions to this equation in the form of a set of

equations (so-called analytic solutions) have
only been obtained for one-electron systems.

– The solutions take the form of a set of wave

functions with associated energies.

– Thus the Schrödinger equation predicts

quantization of atomic properties as a natural
consequence of the wave-nature of an electron
moving at high velocity in the central force-
field of a nucleus within an atom.
65

Solutions to the Schrödinger wave equation

• The Schrödinger equation can be solved

analytically for one-electron atoms.

– However, it is necessary to cast the equation in the

form of spherical polar coordinates, rather than
leaving it in the more familiar Cartesian coordinates
used above.

– This coordinate system is an alternative way to

describe the location of any point in space, and is
ideally suited for spherical systems.

– The point is labeled not by (x,y,z), but by (r, θ, φ),

where these three terms are best defined in a diagram
such as the one shown (next slide)
66

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Boundary conditions
• In principle there are an infinite number of
solutions to the Schrodinger equation.

• If sin(kx) is a solution then so is asin(bkx)

for all values of a and b

67

Boundary conditions
• However only a subset of solutions are
allowed physically and these are determined
by boundary conditions imposed by the
physical situation which the Schrodinger
equation describes

• Examples are shown for a particle in a box

or an electron in a hydrogen atom

• The fact that only certain values of E and 

are allowed for a particular Schrodinger
equation is the origin of the quantization of
energy
68

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Particle in a box
• The application of Schrodinger’s equation
to a particle undergoing one dimensional
translational motion between confined
limits demonstrates how imposition of
boundary conditions gives rise to one
of the fundamental principles of
quantum mechanics, Quantization.
– The two walls of the box are at positions x = 0
and x = l along the x-axis
– Inside the box is a particle of mass (m)
– The particle moves freely in the x-direction,
and the potential energy V=0
69

Particle in a box
– The potential energy rises abruptly to infinity at the walls
• The Schrodinger equation for the particle in the box is:
ℏ2 𝑑 2 
− = 𝐸
2𝑚 𝑑𝑥 2
• A solution to this equation is
2𝑚𝐸
 = 𝑠𝑖𝑛 𝑥
ℏ2
2𝑚𝐸
• The general solution is  = 𝑎𝑠𝑖𝑛 𝑥
ℏ2
– Any value of E and a forms a suitable wave function

70

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Particle in a box
• Because the particle is confined to a box of finite length,
the walls impose boundary conditions on which wave
functions are physically allowable

• Since the potential energy rises to infinity at the walls,

the probability of finding the particle outside the box is
zero, so the wave function at the walls and everywhere
outside the box must be zero.

• Therefore all acceptable wave functions for the particle

must fit exactly inside the box, like the vibrations of a
string fixed at both ends

• To satisfy this condition requires that the wavelength,,

of allowed functions must be one of the values:
71

Particle in a box

2𝐿 2𝐿
 = 2𝐿, 𝐿, , ,…
3 4
2𝐿
• More precisely  = n= 1, 2, 3,…
𝑛
• The relationship between  and the mathematical
description of a sine wave is sin (2/) so the
2𝑚𝐸
wavelength of the wave function  = 𝑎𝑠𝑖𝑛 𝑥 𝑖𝑠
ℏ2

1 ℏ2
=
2 2𝑚𝐸
• Therefore allowed wave function of the particle in a
box must satisfy:
72

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Particle in a box

2𝐿 1 ℏ2
=
𝑛 2 2𝑚𝐸

𝑛2 ℎ 2
• On rearranging it gives 𝐸𝑛 =
8𝑚𝐿2

• The subscript n is added to emphasize the fact that the

particle in the box is only permitted to posses discrete
values, or quanta, of E corresponding to integer values of
n in the above expression.

• The allowed energies of a system are called the energy

levels
73

Particle in a box
• The wave functions associated with these energies are:
2𝑚𝐸𝑛 𝑛
𝑛=𝑎𝑠𝑖𝑛 2
𝑥 = 𝑎 𝑠𝑖𝑛 𝑥
ℏ 𝐿
• The constant a is chosen so that the total probability of finding the
particle in the region x=0 to x= L is 1, which gives 𝑎 = 2𝐿

• The integer n in the equations is the allowed energies and wave

functions of the particle is an example of a quantum number.

• All wave numbers (except 1) have nodes where there is zero
probability of finding a particle at these points

• The most probable location of a particle is midway between the

walls

74

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Zero Point Energy

• The lowest energy a system is allowed to possess
corresponds to the lowest quantum number of the
system
• For the particle in a box, that is n=1
𝑕2
𝐸1 =
8𝑚𝐿2
• This intrinsic energy is called the zero point energy

• Existence of zero point energy is a manifestation of the

uncertainty principle because if a particle is confined to
a finite space its momentum and hence kinetic energy
can not be zero (there is no zero point energy for a
particle in a circular orbit)
75

Particle in a Circular Orbit

• Consider a particle of mass m moving in a circular orbit
of radius r with velocity V
– Its linear momentum = mv
– Its angular momentum = mvr

• If the potential energy is zero, then the total energy is

entirely kinetic and given by:
𝑝2 (𝑎𝑛𝑔𝑢𝑙𝑎𝑟 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚)2 (𝑎𝑛𝑔𝑢𝑙𝑎𝑟 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚)2
𝐸= = =
2𝑚 2𝑚𝑟 2 2𝐼
– I = mr2 is called the moment of inertia of a particle about
the center of the path
– The moment of inertia is the rotational equivalent of mass
in linear motion

76

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Particle in a Circular Orbit

• The de Broglie equation
is used to express the
angular momentum of
the particle in terms of
the wavelength of its
associated wave
function
𝑎𝑛𝑔𝑢𝑙𝑎𝑟 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚
𝑕
= 𝑝𝑟 = 𝑟

2
ℎ
𝑟
Hence 𝐸 = 
2𝐼 77

Particle in a Circular Orbit

• The boundary condition of the system is that the
shape of the wave function must repeat after
each circuit of 360 around the circumference of
the trajectory along which the particle travels

• If this condition is not satisfied then the wave

function cancels out, or destructively interferes
on each circuit
• Therefore the physically acceptable wave
functions must have wavelengths:
2𝜋𝑟
= n = 0, 1, 2…
𝑛
• The allowed energy quanta for the particle in a
ring is therefore:
78

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Particle in a Circular Orbit

ℎ𝑛 2
𝑛2 ℏ2
𝐸𝑛 = 2𝜋
= n = 0, 1, 2….
2𝐼 2𝐼
– Positive and negative numbers are allowed
corresponding to circular motion with the same
kinetic energy in either clockwise or anticlockwise
direction
• The corresponding allowed quantized values
of angular momentum are:
ℎ
• 𝑎𝑛𝑔𝑢𝑙𝑎𝑟 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚 =  𝑟 = 𝑛ℏ n = 0,
2 𝑟
𝑛
1, 2….
79

Separation of variables in spherical polar coordinates and resulting

solutions

80

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Separation of variables in spherical polar coordinates

and resulting solutions
• Convert the Schrödinger equation to spherical polar coordinates.
• Then substitute for V the appropriate Coulomb potential for the
one-electron atoms, where Z is the number of protons in the
nucleus:

• This is easy to do using spherical coordinates, but hard in Cartesian

(which is why we will ignored the latter in the further discussion!)

• After the conversion we obtain an immediate bonus, because we

can now separate the differential equation into three sub-functions,
each in terms of one of the defining variables r, θ and φ. We call the
r function R, the θ function Θ, and the φ function Φ (i.e. using
capital Greek letters).

81

Separation of variables in spherical polar coordinates

and resulting solutions

82

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The Wave Nature of Matter - Key notes

• Wave functions and probabilities
• Schrodinger equation
• Boundary conditions
• Heisenberg's uncertainty principle
• Particle in a box
• Particle in a circular orbit

83

The Structure of the Hydrogen Atom

• A hydrogen atom emission spectrum is obtained
by passing an electric discharge through a tube of
low pressure hydrogen gas and dispersing the
emitted light into its constituent wave lengths
using a prism or diffraction grating

• The resulting spectrum consists of light emitted

at discrete frequencies only

• The emitted frequencies  occur in distinct

groups with a regular pattern in different regions
of the electromagnetic spectrum
84

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The Hydrogen Spectrum

85

The Structure of the Hydrogen Atom

• The frequencies
conform to the
expression
1 1
 = 𝑅𝐻 2
− 2
𝑛1 𝑛2
𝑛1 = 1, 2, … .
𝑛2 = (𝑛1
+ 1), (𝑛1 +2), … .
– This sequence is known
as the Rydberg series
and the constant RH =
109677 cm-1 is the
Rydberg constant
86

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Interpretation of the Hydrogen spectrum

• The Rydberg series of lines in the hydrogen emission
spectrum is accounted for by solving the Schrodinger
equation for the electron in the hydrogen atom

• The potential energy V of an electron at a distance r

from a central nucleus of positive charge Ze is
described by the coulomb potential:
𝑍𝑒 2
• 𝑉=−
4ℇ0 𝑟
– 0 is the vacuum permittivity
– For hydrogen Z = 1
– (minus sign) indicates attraction between the opposite
charges of the electron and nucleus
87

Interpretation of the Hydrogen spectrum

• When the electron and the nucleus are infinitely
separated V=0
• The Schrodinger equation for a single particle moving
in this potential energy can be solved exactly
• The imposition of boundary conditions (that wave
functions approach zero at large distance) restricts the
system to certain allowed wave functions and their
associated energy values
• The allowed quantized energy values are given by the
expression:
𝑒 4 𝑍 2
𝐸𝑛 = − 𝑛 = 1, 2 …
80 2 𝑕2 𝑛2
88

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Interpretation of the Hydrogen spectrum

𝑚𝑒 𝑚 𝑛
= is the reduced mass of the electron
𝑚𝑒 +𝑚𝑛
me and nucleus mn
• The energy level formula applies to any one-
electron atom (called hydrogenic atoms) e.g.
H, He, Li2+, Be2+ etc.
• The difference between any pair of energy
levels in hydrogenic atoms is:
𝜇𝑒 4 𝑍 2 1 1
• ∆𝐸 = 𝐸𝑛2 − 𝐸𝑛1 = −
8𝜀0 ℎ 𝑛1 2
2 2 𝑛2 2

89

Atomic Quantum Numbers

• The full solution of the Schrodinger equation for hydrogenic
atoms contains three different quantum numbers to specify
the allowed wave functions and energies of the states of
the electron
– Principle quantum number (n = 1, 2, 3…)
– The orbital angular momentum quantum number (l = 0, 1,2….(n-
1))
– The magnetic quantum number (m = -l…..l)

• Each wave function which is specified by a unique set of

three quantum numbers is called an atomic orbital

• All orbitals with the same principle quantum number n are

said to belong to the same shell

• Orbitals with the same principle quantum number but

different values of l are called subshells 90

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Atomic orbitals
• For hydrogen-like atoms, the wave functions are also called
“atomic orbitals”

• Orbitals of different systems differ only in nuclear charge

(Z)

• Orbitals are denoted by s, p, d, f for l=0,1,2,3…

– Thus we have 1s, 2s, 2p atomic orbitals corresponding to (n=1,
l=0), n=2, l=0), (n=2, l=1) respectively

• For H-like atoms, the energy depends only on ‘n’ and is

independent of ‘l’ and ‘m’
– Thus orbitals having the same n and different l and m are
degenerate
– The hierarchy of energy states is thus*1s+<*2s, 2p+<*3s,3p,3d+….
91

Representing atomic orbitals

• For an atomic system containing one electron (e.g. H, He+
etc.) The wave function  is a solution of the Schrödinger
equation.

• It describes the behavior of an electron in a region of space

called an atomic orbital ( – phi ).

• Each wave function has two parts, the radial part which
changes with distance from the nucleus and an angular part
whose changes correspond to different shapes.

• Orbitals have
– SIZE determined by the radial part of the wave function
– SHAPE determined by the angular part of the wave
function(spherical harmonics)
– ENERGY determined by the Schrodinger equation. (Calculated
exactly for one-electron systems, and by trial and error
manipulations for more complex systems). 92

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Representing atomic orbitals

• To describe the
wave function of
atomic orbitals we
must describe it in
three dimensional
space

• For an atom it is
more appropriate
to use spherical
polar coordinates

93

Graphical representation of orbits

• As principal number n increases the function

oscillates as directed in the polynomial part
– “Nodal” points appear on the r-axis where =0
– The number of nodes for an s=function is n-1

• As nuclear charge increases, the function falls off

more rapidly with r
• For the 1S orbital (n=1, l=0, m =0), the
mathematical form of the wave function is:
𝑟
−
 𝑎
𝑒 0
Where a0 is Bohr’s radius

94

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Graphical representation of orbits

• The wave function contains no angular

dependence so it has the same shape
(exponential decrease) in all directions from the
center of the atom.
• Therefore the 1S orbital is spherically symmetrical
• For the radial part of the wave function, the
probability of finding the electron in the region
between r and r+ dr is given by
𝑟𝑎𝑑𝑖𝑎𝑙 𝑝𝑟𝑜𝑏𝑎𝑏𝑙𝑖𝑙𝑖𝑡𝑦 𝑑𝑖𝑠𝑡𝑟𝑖𝑏𝑢𝑡𝑖𝑜𝑛 𝑓𝑢𝑐𝑛𝑡𝑖𝑜𝑛
= 4𝜋𝑟 2 2 𝑑𝑟
– Where 4r2dr is the volume of the spherical shell of
thickness dr and radius r

95

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Graphical representation of Radial Function

• R(r) of the 1s orbital of
H
• It decays exponentially
with r
• It has a maximum at r =
0
• R(r) has no physical
meaning.
• R(r)2 does.
– It represents the
probability density of
the electron at a point
in space
– R(r)2 is a maximum at r
=0

97

Radial distribution functions

• Relating the probability of an
electron at a point in space to
the probability of an electron in
a spherical shell at a radius r (an
orbit-lke picture)

• This is called the Radial

Distribution Function (RDF) as
in generated by multiplying the
probability of an electron at a
point which has radius r by the
volume of a sphere at a radius
of r

98

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99

Structure of Hydrogen atom- Key notes

• Hydrogen spectrum
• Interpretation of hydrogen spectrum
• Atomic quantum numbers and orbitals
• Shapes of atomic orbitals

100

50