Quantum Theory (CHM3101)

Reference: Atkins, 10th Edition, Chapter 7,8,9

 Quantum Theory

 Introduction
 Energy Quantization
 Black-body Radiation
 Wave-particle Duality
 The Particle Character of Electromagnetic Radiation
 The Wave Character of Particles
 The Schrodinger Equation
 The Uncertainty Principle
 Translational Motion
 A Particle in a One-dimensional Box

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 Introduction
 Classical mechanics; the work done in the areas of chemistry and physics prior to
the 20th century.

 For example, organization of the periodic table, thermodynamics, the wave theory
of light, and Newtonian mechanics which is based on Newton equation of motions.

 Newtonian mechanics; Using laws of motion introduced by Newton

(macroscopic bodies)

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 Newtonian mechanics;

• predicts a precise specified location and momentum at any time (trajectory) for a
particle.

• Momentum is a product of the mass & velocity of an object (p = mv).

• allows the translational, rotational, & vibrational modes of motion to be excited to any
specified energy by controlling the force.

• But it fails when it comes to transfer very small energy or objects with very small
mass.

• Therefore, Quantum mechanics (QM) was born out because of the inability of classical
mechanics to reconcile theory with experiment.

• For example, blackbody radiation, the photoelectric effect, and heat capacity were
among the experiments that can not be explained by classical mechanics.

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 Electromagnetic spectrum:

 Light is an electromagnetic radiation in the visible region of the spectrum.

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 It can be understood in terms of
electromagnetic field.

 Electromagnetic field is an oscillating electric

and magnetic disturbance that spreads as a
harmonic wave.

 Two concepts; electric field (acts on charge

particles) and magnetic field (acts on moving
charged particles).

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 The wavelength (λ ) of electromagnetic radiation is the distance from
the top (crest) of one wave to the top of the next wave.

o Measured in units of distance such as m,cm, Å.

o 1 Å = 1 x 10-10 m = 1 x 10-8 cm

 The frequency (ν) of electromagnetic radiation is the number of crests or

troughs that pass a given point per second.

o Measured in units of 1/time; s-1

o 1 Hertz (Hz) = 1 s-1
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 The wave travels at a constant speed of light, c, 3 ×108 m.s-1.

 Therefore; 𝜆𝜈=c

 1
 Wave is usually characterized by wavenumber (cm-1):   
c 

 Example: What is the frequency of green light of wavelength 5200 Å?

c
c     

 1 x 10-10 m  -7
  (5200 Å)    5.200  10 m
 1Å 
3.00  108 m/s 14 -1
 -7
 5.77  10 s
5.200  10 m
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 Energy Quantization: Black-body Radiation

A hot object such as a heated metal bar emits radiation.

This sort of radiation is called “black-body” radiation.

Black body is an object capable of emitting and absorbing all

wavelength of radiation uniformly.

The term "black body" is used because the intrinsic color of

the material is not important. It means that a bar of gold and a
bar of black graphite at 3000 °C would emit the same color.

In below picture an iron bar is heated from left to right. Gas welding
Explain what is happening with increasing the temperature.

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 To explain this effect, the concept of the density of
energy, dE*, was used.

 dE*, by definition is the total energy in a region of

the electromagnetic field divided by the volume of
the region (J.m-3).
d    , T      , T  d 

 ρ is called density of states (J.m-4).


 Therefore:  T       , T d 
0

 It means that the higher the temperature, the

greater the energy density (the area under the
curve).

 Also, notice to the shift of the peaks to the lower

wavelength.
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 But Lord Rayleigh thought of electromagnetic field as a collection of
oscillators of all possible frequencies.

 He knew that the average energy of each oscillator, regardless of its

frequency is kbT. kb is a Boltzmann constant (kb= 1.3806503 × 10-23 m2 kg s-2
K-1).

 Therefore, he suggested the Rayleigh-Jeans law for density of states:

8 kbT
  , T  
4
 But it failed at short wavelengths (high frequencies).

 A large amount of energy is radiated in the

high-frequency region which is called
ultraviolet catastrophe.

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 Max Plank proposed a successful approach.

 Light has a particle character & energy is quantized.

 It means that the energy is limited to discrete values

& can not be varied arbitrarily.

 He called them as quanta or photons.

 This limitation was called quantization of energy.

Planck’s equation is;
  nh
 h is Plank`s constant (h = 6.626 × 10-34 J.s) and n = 1,2,…

 This was opposite with the viewpoint of classical

mechanics. So, he derived Plank distribution as:

8 hc
  , T  
 5  e hc  kT  1
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 Atomic Structure and Atomic Spectra

H2 Emission Spectrum

Line Emission Spectrum of Hydrogen Atoms

The fact that the emission spectra of H 2(g) and other molecules is a line rather than continuous
emission spectra tells us that electrons are in quantized energy levels.
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 Rydberg
constant
1
𝜆
=𝑅
(1
𝑛1
2
−
1
𝑛2
2
)

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Calculate the frequency of light emitted for an electron transition from the
sixth to third orbit of the hydrogen atom. In what region of the spectrum
does the light occur? (R = 109678 cm-1; c = 3.00 x 108 m/s)

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Calculate the frequency of light emitted for an electron transition from the
sixth to third orbit of the hydrogen atom. In what region of the spectrum
does the light occur? (R = 109678 cm-1; c = 3.00 x 108 m/s)

1
𝜆
=𝑅
1
−
(1
𝑛12 𝑛 22 )
1
( )
1 1
=𝑅 2 − 2 =( 109678 ) × ( 0.0833 )=9139.8cm
𝜆 3 6
−1

???

The line is in the visible spectrum of hydrogen. It is part of the Paschen series
because the electron has had a transition from higher orbit to the second orbit.

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 Wave-Particle Duality

Spread in space (wavelength) and time

Waves (frequency)

Can be superposed – show interference

effects (Pass through
each other).

Localized in space and time. Ball, Car, person,

or point like objects called particles.
Particles
Cannot pass through each other - they
bounce or shatter.

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 The Particle Character of electromagnetic radiation: photoelectric effect

 When UV light is shone on a metal plate in a vacuum,

it emits charged particles (Hertz, 1887), which were
later shown to be electrons by J.J. Thomson (1899).

 No electrons will be ejected, unless its frequency

exceeded a threshold value characteristics of the
metal.

 It means that the maximum kinetic energy, KE , of

ejected electrons is independent of intensity, but
dependent on frequency, ν.

 Thus, the kinetic energy of the ejected electrons

increases linearly with the frequency of the radiation
but is independent of the intensity of the radiation.

 This was the situation facing physicists in 1905. So,

Albert Einstein made the bold assertion that light is
made up of particles (later called photons).
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 If the projectile is a photon of energy, then the
conservation of energy requires that the kinetic
energy of the ejected electron should obey:

1
me v 2  h  
2

– Phi is the characteristic of the metal, work

function. Work function is the minimum
energy needed for electron to escape from
metal (depends on material, but usually 2-
5eV)

 Photo-ejection can not occur if h𝜈 < Φ Because

there is no sufficient energy for photon.

 The equation predicts that the kinetic energy

of an ejected electron should increase linearly
with frequency.

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 The Wave Character of a Particle
 In 1923, Prince Louis de Broglie postulated that any particle, not only photons which
travelling with a linear momentum (p=mv) can have wave-like properties. The
wavelength given by de Broglie relation as λ = h/p; h is Plank constant (6.6262x10-34 J.s).

 From the equation, wavelength depends on momentum, not on the physical size of
the particle. As a result, we can see diffraction and interference of matter waves.

 The Davisson-Germer experiment (1927); They found a pattern of sharp reflected

beams from the Ni crystal at fixed accelerating voltage (fixed electron energy). Davisson
got the 1937 Nobel prize because of this experiment.

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 G. P. Thomson performed similar interference experiments with thin-film
samples.

 They found that the diffraction of electrons by a crystal is similar to

Bragg scattering of X-rays from crystals.

 Now, we are in the heart of modern physics. At atomic scales, the

classical concepts of particle and wave melt together; particles taking on
the characteristics of waves, and waves taking on the characteristics of
particles.

 This joint particle and wave character of matter and radiation is called
wave-particle duality.

 Heisenberg Uncertainty Principle; one of the most celebrate results of

quantum mechanics. It is impossible to specify simultaneously, with
arbitrary precision, both the momentum and position of a particle.

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 The Schrodinger Equation
Erwin Schrodinger proposed an equation to find the wavefunction of the system.

Based on classical mechanics, trajectory is the path in which a moving object

follows through space as a function of time.

The mathematical representation of the wave in quantum mechanics (QM)

replaces the classical concept of trajectory with a wavefunction, 𝜓.

The general time-independent Schrodinger equation;

Ĥ   

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23
 The Schrodinger equation is: Ĥ   

 The quantity with hat is an operator which plays a special role in QM.

(the energy operator)(wavefunction/eigenfunction)=(eigenvalue)(wavefunction/eigenfunction)

 The Hamiltonian operator (H-hat) corresponds to the total energy of the system.

(the energy operator/Hamiltonian) Ψ = (the total energy)× Ψ

 An observable is a measurable properties of a system, so:

(an operator corresponding to an observable) Ψ = (the value of observable)× Ψ

 An observable is a property of the system that can be determined by some sequence

of physical operations. For example, Hamiltonian is an observable.

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 For a particle of mass, m, moving in one dimension with energy, E, which does not
change with time, Schrodinger equation can be written as;

 2 d 2 ( x )
  V  x  ( x )   ( x )
2m dx 2

 V(x) is the potential energy of particle at point x. As you can see the potential energy, V, depends on the
position.

 Since Etot=Ek+Ep, the other part must be related to the kinetic energy of the particle.

 Therefore, rather than saying a particle has a specified position and momentum, we
instead describe it by a wavefunction.

 Wavefunction is a function of all the coordinates of the particle [ 𝜓(x,y,z)] . For

example, in one-dimension (x);
 ( x)

x
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 The Particle in a ‘Box’; Translational Motion

 Imagine that we have particle (e.g. an

electron) in a one-dimensional box with
impenetrable walls. It means that you
have a sufficiently high barrier.

 Potential energy is zero between x = 0

and x = L, rises sharply to infinity at the
walls.

, x  0, x  L
V ( x)  
 0, 0 x L

 Thus, 𝜓(0)= 𝜓(L)= 0 (there is no

wavefunction defined at the wall).

 This reflects the boundary conditions

imposed by the potential V(x).
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 The Schrödinger equation for the one-dimensional box can be written as,

d 2  2mE 
    0
dx 2  
2

 Because the particle must remain in the box, the Schrödinger equation will be
solved such that the wavefunction will look like; (n is energy level & L is the
length of box
 n x 
 1  C sin  
 L 
 We can use this wavefunction to calculate the probability that the particle in
level n is at position x.

 To determine the constant C, recall that all probabilities must be equals to one
because the particle must be somewhere in the box. Therefore, the final
wavefunction will look like:
2  n x 
 ( x)  sin  
L  L 

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 After solving the Schrodinger equation using the wavefunction obtained,
you will find that, the energy of the particle depends directly on the
value of n (principle quantum number)(n= 1,2,3,...).

n 2 2  2 n2 h2
En  2

8mL 8mL2
h2
En 1  En   2n  1
8mL2
h2
E0   En 1  
8mL2

 It means that the energy is quantized. There are allowed energy levels for
a particle in a box.

 Note that the energy levels increase as n2. Also, their separation increases
as the quantum number increases.
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 Thus, the total energy of the n-th level can be expressed in term of the
ground state energy as En= n2E0 (n= 1,2,3,...)

 The lowest energy level (n=1) is called ground state, the others are called
excited states. These are very important concepts in spectroscopy.

 Therefore, the lowest possible energy for a particle in the box is not zero
but E0 (= E1 ), the zero-point energy.

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 This result is also consistent with the Heisenberg uncertainty principle.

 The ‘particle’ is no more pictured as a particle bouncing between the

walls. It is a de Broglie wave (λ = h/P) that is trapped inside the infinite
quantum well, in which they form waves.

 Recall that λ is wavelength, h is Plank’s constant, and P in linear

momentum.

 For example; look at the following slide. you can see the first three
wavefunctions and the corresponding probability distributions.

 Note that the probability density is zero at the boundaries. The particle
spend most of its time in places where its probability to be found is
largest.

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  n=3 is the second
excited state, 4 nodes,
3 antinodes.

2 nx 
 x   sin 
L  L 

  n=2 is the first

excited state, 3 nodes,
2 antinodes.

 n=1 is the ground

state: 2 nodes, 1
antinode.

E y y*y 31
 Application
 Consider the following dye molecule. The length of the molecule is
the length of the “box” in which an electron is limited to move:

+
N

L=8Å
N

 What wavelength of light corresponds to 𝛥E from n=1 to n=2?

h2 h2
2  final initial  2  
2 2 2 19
E  n  n  2  1  2.8  10 J
8mL 8m(8)
c
E  h  h    700nm

(experimental value: 680 nm)
 p orbitals

 Consider 2p orbitals. You have 3 degenerate orbitals (l=1; ml=0,±1).

 It means that the electron has different angular momentum around an

arbitrary z-axis but the same magnitude of that momentum.

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 d orbitals
 d orbitals are also formed in the same way, by taking linear combinations of the
orbitals with opposite values of ml (l=2; ml= 0,±1,±2).

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