THANIA VAZQUEZ

CHAPTER 2: QUANTUM THEORY AND ATOMIC STRUCTURE

Light: Electromagnetic Waves, the Electromagnetic Spectrum and Photons

ELECTROMAGNETIC WAVES
Electromagnetic radiation is one of the many ways that energy travels through space.
Examples: heat from a burning fire, light from the sun, x-rays in diagnostics, microwave
BASIC PROPERTIES OF WAVES: amplitude, wavelength, frequency and speed

 A wave has a trough (lowest point) and a crest (highest point).

 The vertical distance between the tip of a crest (or trough) and the wave’s central axis is known as
its amplitude (A). This is the property associated with the brightness, or intensity, of the wave.
 The horizontal distance between two consecutive troughs or crests is known as the wavelength (𝝀) of
the wave.

The wave’s frequency (𝝂 ("𝑛𝑦𝑢") 𝑜𝑟 𝒇 𝑖𝑛 𝑠𝑜𝑚𝑒 𝑏𝑜𝑜𝑘𝑠) refers to the number of full wavelengths that pass by a
1
given point in space every second. The unit is 𝑜𝑟 𝑠 −1. The SI unit is Hz.
𝑠

TIME = 1S

The speed of the electromagnetic wave (light) is given by

𝒄 = 𝝀𝝂

where 𝝀 is the wavelength in meter, 𝝂 is in Hz or 𝒔−𝟏 and 𝒄 is the speed of light in vacuum equivalent to
𝒎
𝟑𝒙𝟏𝟎𝟖 𝒔 .

Wavelength (𝜆) and frequency (𝜈) are inversely proportional: that is, the shorter the wavelength, the higher the
frequency, and vice versa.
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Example: Calculating the wavelength of a light wave

A particular wave of electromagnetic radiation has a frequency of 1.5 𝑥 1014 𝐻𝑧.
What is the wavelength of this wave?

THE ELECTROMAGNETIC SPECTRUM

Electromagnetic waves can be classified and arranged according to their various wavelengths/frequencies; this
classification is known as the electromagnetic spectrum.

VISIBLE SPECTRUM
Violet: 400 – 420 nm Green: 490 – 570 nm Red: 620 – 780 nm
Indigo: 420 – 440nm Yellow: 570 – 585 nm
Blue: 440 – 490 nm Orange: 585 – 620 nm

QUANTIZATION OF ENERGY AND THE DUAL NATURE OF LIGHT

According to classical physics, matter was composed of particles that have mass, and whose position in
space could be known; light waves, on the other hand, were considered to have zero mass, and their position
in space could not be determined.
This all changed in 1900, however, when the physicist Max Planck began studying blackbodies – bodies
heated until they began to glow. Planck found that the electromagnetic radiation emitted by blackbodies could
not be explained by classical physics, which postulated that matter could absorb or emit any quantity of
electromagnetic radiation.
Planck observed that matter actually absorbed or emitted energy only in whole-number multiples of the
value 𝒉𝝂 where 𝒉 = 𝟔. 𝟔𝟐𝟔𝒙𝟏𝟎−𝟑𝟒 𝑱. 𝒔 is the Planck’s constant and 𝝂 is the frequency of the light absorbed or
emitted. The Planck’s equation is
𝑬 = 𝒉𝝂
Energy is not continuous but quantized—meaning that it can only be transferred in individual “packets” (or
particles) of the size 𝒉𝝂. Each of these energy packets is known as a quantum (plural: quanta).
Since c=λν, then
𝒉𝒄
𝑬=
𝝀
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PHOTON

At the beginning of the twentieth century, the discovery that energy is quantized led to the revelation that light
is not only a wave, but can also be described as a collection or streamed of particles known as photons. A
photon is the elementary particle, or quantum, of light. Photons carry discrete amounts of energy called
quanta.
When a photon is absorbed, its energy is transferred to that atom or molecule. Because energy is
quantized, the photon’s entire energy is transferred.

When an atom or molecule loses energy, it emits a photon that carries an energy exactly equal to the loss in
energy of the atom or molecule.
(Remember that we cannot transfer fractions of quanta, which are the smallest possible individual
“energy packets”.)
Example: Calculating the energy of a photon
A photon has a frequency of 2.0 𝑥 1024 𝐻𝑧.
What is the energy of this photon?

Concept check:
As the wavelength of a photon increases, what happens to the photon's energy?

Concept check:
The wavelength of orange light is about 590-635 nm and the wavelength of green light is about 520-560 nm.
Which color of light is more energetic, orange or green?
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PHOTOELECTRIC EFFECT

When light shines on a metal, electrons can be ejected from the

surface of the metal in a phenomenon known as the photoelectric
effect or often referred to as photoemission.
 In terms of their behavior and their properties,
photoelectrons are no different from other electrons.
 The prefix, photo-, simply tells us that the electrons have
been ejected from a metal surface by incident light.
 Albert Einstein proposed this model that light sometimes
behaved as particles of electromagnetic energy which we
call photons.

We can think of the incident light as a stream of photons with an energy determined by the light frequency.
When a photon hits the metal surface, the photon's energy is absorbed by an electron in the metal.
Below illustrates the relationship between light frequency and the kinetic energy of ejected electrons.
The frequency of the red light is less than the threshold frequency (minimum frequency to eject electrons) of
the metal K, thus no electrons were being ejected. Furthermore, the kinetic energy of the photoelectrons was
proportional to the light frequency.

The total energy of the incom ing photon, Ephoton, must be equal to the kinetic energy of the ejected electron,
KEelectron, plus the energy, E0, required to eject the electron from the metal. The energy required to free the
electron from a particular metal is also called the metal's work function (different metals have different E0).

In terms of the light frequency using Planck's equation:

Rearranging we get,

𝑤ℎ𝑒𝑟𝑒 𝒎𝒆 = 𝟗. 𝟏𝟎𝟗 𝒙 𝟏𝟎−𝟑𝟏 𝒌𝒈

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 We can analyze the frequency relationship using the law of conservation of energy.
 Einstein used Planck's results to explain why a minimum frequency of light was required to eject electrons
from a metal surface.
 We can see that kinetic energy of the photoelectron increases linearly with frequency nyu as long as the
photon energy is greater than the work function.

BOHR'S MODEL OF HYDROGEN

At the beginning of the 20th century, a new field of study known as quantum
mechanics emerged. One of the founders of this field was Danish physicist
Niels Bohr, who was interested in explaining the discrete line spectrum
observed when light was emitted by different elements.
Bohr was also interested in the structure of the atom, which was a topic of
much debate at the time. Numerous models of the atom had been postulated
based on experimental results including the discovery of electrons by J.J.
Thompson and the discovery of nucleus by Ernest Rutherford.
Bohr supported the planetary model, in which electrons revolved around a
positively charged nucleus like the planets around the sun.
However, scientists still had many unanswered questions:
 Where are the electrons, and what are they doing?
 If the electrons are orbiting the nucleus, why don’t they fall into the nucleus as predicted by classical
physics?
 How is the internal structure of the atom related to the discrete emission lines produced by excited
elements?
Bohr addressed these questions using a seemingly simple assumption:
 What if some aspects of atomic structure, such as electron orbits and energies, could only take on
certain values?

ATOMIC LINE SPECTRA

Atomic line spectra are another example of quantization.

When an element or ion is heated by a flame or excited by electric current, the excited atoms emit light of a
characteristic color.
The emitted light can be refracted by a prism, producing spectra with a distinctive striped appearance due to
the emission of certain wavelengths of light.
When something is quantized, it means that only specific values are allowed.
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Thus, emission spectra are produced by thin gases in which the atoms do not experience many collisions
(because of the low density). The emission lines correspond to photons of discrete energies that are emitted
when excited atomic states in the gas make transitions back to lower-lying levels.
A continuum spectrum results when the gas pressures are higher. Generally, solids, liquids, or dense gases
emit light at all wavelengths when heated.
An absorption spectrum occurs when light passes
through a cold, dilute gas and atoms in the gas
absorb at characteristic frequencies; since the re-
emitted light is unlikely to be emitted in the same
direction as the absorbed photon, this gives rise to
dark lines (absence of light) in the spectrum.
The lines on the emission or absorption spectrums
of an element are produced when the electrons in
that atom change energy levels.

According to Bohr's model,

 An electron would absorb energy
in the form of photons to get
excited to a higher energy
level as long as the photon's
energy was equal to the energy
difference between the initial and
final energy levels.
 After jumping to the higher energy
level—also called the excited
state—the excited electron would
be in a less stable position, so it
would quickly emit a photon to
relax back to a lower, more stable
energy level.
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We can also find the equation for the wavelength of the emitted electromagnetic radiation using:

where 𝑹 is the Rydberg constant equivalent to 𝟏. 𝟎𝟗𝟕 𝒙 𝟏𝟎𝟕 𝒎−𝟏 .

The equation says that the frequency—and wavelength—of the emitted photon depends on the energies of the
initial and final shells of an electron in hydrogen.

What have we learned since Bohr proposed his model of hydrogen?

 The Bohr model worked beautifully for explaining the hydrogen atom and other single electron
systems such as He+.
 However, it failed to explain the electronic structure in atoms that contained more than one electron.
 Furthermore, the Bohr model had no way of explaining why some lines are more intense than others or
why some spectral lines split into multiple lines in the presence of a magnetic field—the Zeeman effect.

In the following decades, work by scientists such as Erwin Schrödinger showed that electrons can be
thought of as behaving like waves and behaving as particles. This means that it is NOT possible to know
both a given electron’s position in space and its velocity at the same time, a concept that is more
precisely stated in Heisenberg's uncertainty principle. Instead, we can only calculate probabilities of
finding electrons in a particular region of space around the nucleus.

THE QUANTUM MECHANICAL MODEL OF THE ATOM

WAVE-PARTICLE DUALITY AND THE DE BROGLIE WAVELENGTH

Another major development in quantum mechanics was pioneered by French physicist Louis de Broglie. Based
on work by Planck and Einstein that showed how light waves could exhibit particle-like properties.
Louis de Broglie hypothesized that particles could also have wavelike properties.
De Broglie derived the following equation for the wavelength of a particle of mass m (in kg), traveling at
velocity u (in m/s),

 Note that the de Broglie wavelength and particle mass are inversely proportional.
 The inverse relationship is why we don't notice any wavelike behavior for the macroscopic objects we
encounter in everyday life.
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Austrian physicist Erwin Schrödinger theorized that the behavior of electrons within atoms could be explained
by treating them mathematically as matter waves:

̂ is Hamiltonian Operator and 𝜓 is the wave function, and E is the binding energy of electron.
𝐻
This model, which is the basis of the modern understanding of the atom, is known as the quantum
mechanical or wave mechanical model.

Schrodinger’s findings:
 He determined the probability location of electrons in atoms.
 Electrons stuck in their orbits would set up "standing waves".
 He said that you could describe only the probability of where an
electron could be, it was not definite.
 The distributions of these probabilities formed areas of space about the nucleus were called orbitals.
 An orbital is a wave function describing the state of a single electron in an atom.

Due to the Heisenberg uncertainty principle, it is impossible to know for a given electron both its position
and its energy.

The wave functions that are derived from Schrödinger's equation for a specific atom are also called atomic
orbitals.
Chemists define an atomic orbital as the region within an atom that encloses where the electron is likely to be
90% of the time.

QUANTUM NUMBERS OF AN ATOMIC ORBITALS

is used to describe an electron’s behavior or most likely its location.

FOUR QUANTUM NUMBERS

 Principal quantum number (𝑛)- is a positive integer (1, 2, 3,…); indicates
the relative size of the orbital and therefore the relative distance from the
nucleus.
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 Angular Momentum Quantum Number (𝒍) is an integer from 𝟎 𝒕𝒐 (𝒏 − 𝟏); related to the shape of the
orbital.

 Magnetic Quantum Number (𝒎𝒍 ) is an integer from −𝒍 𝒕𝒉𝒓𝒐𝒖𝒈𝒉 𝟎 𝒕𝒐 + 𝒍; prescribes the three-
dimensional orientation of the orbital in the space around the nucleus.

 Spin Quantum Number (𝒎𝒔 )- describes the angular momentum of an electron. An electron spins
around an axis and has both angular momentum and orbital angular momentum.
𝟏 𝟏
Electron’s spin magnitude and direction is + (𝒔𝒑𝒊𝒏 𝒖𝒑 )𝒐𝒓 − (𝒔𝒑𝒊𝒏 𝒅𝒐𝒘𝒏).
𝟐 𝟐