Lecture Presentation

Chapter 2

The Quantum-
Mechanical Model
of the Atom

Catherine E. MacGowan
Armstrong State University
© 2018 Pearson Education, Inc.
 Quantum Mechanics:
The Atomic Model that Explains the Strange
Behavior of Electrons
• Early twentieth century scientists begin investigating the
absolutely small (quantum) world of matter.
– Scientists: Albert Einstein, Neils Bohr, Louis de Broglie, Max
Planck, Werner Heisenberg, P. A. M. Dirac, and Erwin
Schrödinger

• Their investigative work laid the foundation of our current

understanding of matter and its behavior at the subatomic
(absolutely small) level.
– Subatomic particles of matter: electrons, protons, neutrons

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 Quantum Mechanics: The Atomic Model that
Explains the Strange Behavior of Electrons
• They discovered the following:
– Absolutely small matter (extremely small pieces of matter,
such as the electron) behaved MUCH differently than matter
of the macroscopic (large, such as an element or a
molecule) world.

– Absolutely small matter behaved strangely:

• Subatomic particles appeared to exist in two conditions;
they had a natural duality.
– Example: The electron presented particulate behavior (mass,
volume) under a set of experimental conditions and exhibited
energy-like characteristics under a different set of experimental
parameters.
• Wave–matter duality concept

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 The Behavior of Very Small Particles

• Electrons are incredibly small pieces of matter.

– The number of electrons in a single speck of dust is
higher than the number of people who have ever lived
on Earth.
– Directly observing electrons in the atom is impossible;
the electron is so small that observing it changes its
behavior.
• Even shining a light on the electron would affect it.

• Much of the behavior of atoms is determined by

the electron.

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 What Does the Quantum Mechanical Model
Tell about an Atom’s Electrons?
• It explains the manner in which electrons exist and
behave in atoms.
– It is the light wave (energy) nature, not the particulate
(matter) characteristics of the electron, that dictates/
explains the chemical and physical properties
of matter.
– The electron can no longer be viewed as a small piece
of matter orbiting around the nucleus but as a cloud of
most probable positions.

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 What Does the Quantum Mechanical Model
Tell about an Atom’s Electrons?
• It forms the foundation of chemistry by explaining:
– The periodic table—its trends
– The behavior of elements in chemical bonding
– The colors of the atoms and also their size

• It predicts the atomic properties that are directly related to

the behavior of the electrons:
– Why some elements are metals and others are nonmetals
– Why some elements gain one electron when forming an
anion, whereas others gain two
– Why some elements are very reactive, while others are
practically inert
– Why in other periodic patterns we see the properties of
the elements
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 The Nature of Light: Its Wave Nature

• Light is
– A form of electromagnetic radiation
– Composed of perpendicular oscillating waves, one for the
electric field and one for the magnetic field
• An electric field is a region where an electrically charged
particle experiences a force.
• A magnetic field is a region where a magnetized particle
experiences a force.

• All electromagnetic waves move through space at

the same constant speed.
3.00 × 108 m/s = the speed of light

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 Electromagnetic Radiation: Oscillating
Electric and Magnetic Field Waves

Electromagnetic radiation can be described as a wave

comprising oscillating electric and magnetic fields that are
perpendicular within their planes.

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 What Are the Characteristics of Energy
Waves?
• Amplitude:
– The height of the wave
– The distance from node to
crest or node to trough
– The amplitude is a measure of
light intensity—the larger the
amplitude, the brighter the light.
• Wavelength (λ or lambda):
– A measure of the distance
covered by the wave
– The distance from one crest to
the next, the distance from one
trough to the next, the distance
between alternate nodes
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 Amplitude and Wavelength

• Wavelength and
amplitude are
independent properties.

• The wavelength of light

determines its color
(intensive physical
property).

• The amplitude, or
intensity, determines its
brightness (extensive
physical property).

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 Color

• The color of light is determined by its wavelength or

frequency.

• White light is a mixture of all the

colors of visible light.
– A spectrum
– Red Orange Yellow Green
Blue Indigo Violet

• When an object absorbs some of the wavelengths of white

light and reflects others, it appears colored; the observed
color is predominantly the colors reflected.

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 What Are the Characteristics of Energy
Waves?
• Frequency (𝜈 or nu):
– The number of waves that pass a point in a given period
of time
• The number of waves = the number of cycles.
• Units are hertz (Hz) or cycles/s = s −1 (1 Hz = 1 s−1).

• Total energy (E):

– Proportional to the amplitude of the waves and their
frequency
• The larger the amplitude, the more force it has.
• The more frequently the waves strike, the more total force
there is.

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 The Relationship Between Wavelength and
Frequency
• Waves traveling at the same speed will have a shorter
wavelength, so they pass more frequently.
– Meaning: The wavelength and frequency of
electromagnetic waves are inversely proportional.
• Long wavelength → low frequency
• Short wavelength → high frequency

– Mathematically:

– Because the speed of light is constant, if we know the

wavelength we can find the frequency, and vice versa.

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 Problem Solving: Wavelength versus
Frequency
Example Wavelength and Frequency

A laser dazzles the audience at a rock concert by emitting green light with a
wavelength of 515 nm. Calculate the frequency of the light.

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 Electromagnetic Spectrum

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 The Electromagnetic Spectrum

• Visible light (400 to 700 nm) comprises only a small

fraction of all the wavelengths of light, called the
electromagnetic spectrum.

• Shorter wavelength (high-frequency) light has

higher energy.
– Radio-wave light has the lowest energy.
– Gamma-ray light has the highest energy.

• High-energy electromagnetic radiation (e.g., UV, X-ray,

gamma) can potentially damage biological molecules.
– Ionizing radiation

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 Wave Behavior Properties: Interference
• The interaction between waves (e.g., electromagnetic,
ocean) is called interference.

• Interference Types:
– Constructive interference: Waves that interact so that they add
to make a larger wave are said to be in phase.

– Destructive interference: Waves that interact so that they cancel

each other are said to be out of phase.

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 Wave Behavior Properties: Diffraction
• When traveling waves encounter an obstacle or opening in a barrier
that is about the same size as the wavelength, they bend around it; this
is called diffraction.
– Traveling particles do not diffract.
• The diffraction of light through two slits separated by a distance
comparable to the wavelength results in an interference pattern of the
diffracted waves.
• An interference pattern is a characteristic of all light waves.

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 Two-Slit Interference
• As light is passed through two slits, two interfering waves result.

• The difference in path length that the light travels determines if

the interference will be constructive or destructive in nature.

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The Nature of Energy

The wave nature of light

does not explain how
an object can glow
when its temperature
increases.

Electronic
Structure
of Atoms
© 2012 Pearson Education, Inc.
 Ultraviolet Catastrophe

http://en.wikipedia.org/wiki/Ultraviolet_catastrophe
 The Nature of Energy

Max Planck solved the mathematical problem

by assuming that energy comes in packets
Electronic
(later called quanta). Structure
of Atoms
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 Einstein and the Photoelectric Effect
• Einstein observed that when light is shined on a metal surface,
electrons are produced from the surface.
– The electrons emitted from the metal surface are photoelectrons.
– This phenomenon is called the photoelectric effect.

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The Photoelectric Effect

Electronic
Structure
of Atoms
© 2012 Pearson Education, Inc.
 Explaining the Photoelectric Effect
• Classic theory explanation:
– The photoelectric effect according to classic wave theory
attributed the electrons’ being emitted from the metal
surface to the light energy being transferred to the
electrons.
• Classic theory states the following:
– If the wavelength of light is made shorter or the light wave’s
intensity is made brighter, more electrons should be ejected.
– Energy of a wave is directly proportional to its amplitude and
its frequency.
• Example: If a dim light is used, there should be a lag
time before electrons are emitted in order to give the
electrons time to absorb enough energy.

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 Explaining the Photoelectric Effect
• Einstein’s explanation:
Quantum theory
– Experimental
observations indicate the
following:
• A minimum frequency was
needed before electrons
would be emitted
regardless of the intensity,
called the threshold
frequency.
• High-frequency light from a
dim source caused
electron emission without
any lag time.

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 Explaining the Photoelectric Effect
• Einstein’s explanation: Quantum theory
– Einstein proposed that the light energy was delivered to the atoms
in packets called quanta or photons.

Energy = (h𝜈)
quanta
– The energy of a photon of light is directly proportional to
its frequency.

E = hc/λ
• Or it is inversely proportional to its wavelength

– Symbols:
• Planck’s Constant, (h) is a proportionality constant with a
value of h = 6.626 × 10−34 J ∙ s.
• Speed of light (c) value is 3.00 × 108 m/s
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 Einstein’s idea: “Light Is Quantized.”
Ejection of electrons from a metal surface by light:
– One photon at the threshold frequency gives the
electron just enough energy for it to escape the atom.
• Binding energy, ϕ
– When irradiated with a shorter wavelength photon,
the electron absorbs more energy than is necessary
to escape.
– This excess energy becomes kinetic energy of the
ejected electron.
Kinetic Energy = Ephoton – Ebinding
KE = h𝜈 − ϕ
– Where (h𝜈) is a quantized packet of energy

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 A metal will eject electrons from its surface
when struck by yellow light.

Question: What will happen If the surface is

struck with ultraviolet light?
1. No electrons will be ejected.

2. Electrons will be ejected, and they will have the same

kinetic energy as those ejected by yellow light.

3. Electrons will be ejected, and they will have greater

kinetic energy than those ejected by yellow light.

4. Electrons will be ejected, and they will have lower

kinetic energy than those ejected by yellow light.
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 A metal will eject electrons from its surface
when struck by yellow light.

Answer: What will happen If the surface is

struck with ultraviolet light?
1. No electrons will be ejected.

2. Electrons will be ejected, and they will have the same

kinetic energy as those ejected by yellow light.

3. Electrons will be ejected, and they will have greater

kinetic energy than those ejected by yellow light.

4. Electrons will be ejected, and they will have lower

kinetic energy than those ejected by yellow light.
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 Problem Solving: E = hc/λ
Example Photon Energy
The energy required to dislodge electrons from sodium metal via the photoelectric effect
is 275 kJ/mol. What wavelength (in nm) of light has sufficient energy per photon to
dislodge an electron from the surface of sodium?

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 Energy (h𝜈)
Atomic Spectra: When Atoms Absorb

• When atoms or molecules absorb energy, that energy is

often released as light energy.
– Fireworks, neon lights, etc.

• When that emitted light is passed through a prism, a pattern

of particular wavelengths of light is seen that is unique to
that type of atom or molecule.
– The pattern is called an emission spectrum.
• Non-continuous or line spectra
• Continuous or white light spectra

• Line spectra can be used to identify the elements present in

a material as each element has its own unique line spectra.
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 Emission Spectra of Hydrogen

• Elements have their own unique spectrum.

• Example:
– Hydrogen has four distinct lines in its visible spectrum.
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 Examples of Elemental Line Spectra in the
Visible Region

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 The Bohr Model of the Atom

• The nuclear model of the atom (Rutherford model) does

not explain what structural changes occur when the atom
gains or loses energy.

• Bohr developed a model of the atom to explain how the

structure of the atom changes when it undergoes energy
transitions.

• Bohr’s major idea was that the energy of the atom was
quantized, and that the amount of energy in the atom was
related to the electron’s position in the atom.
– Quantized means that the atom could have only very
specific amounts of energy.

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 Bohr’s Model

• The electrons travel in orbits that are at a fixed distance

from the nucleus.
– Stationary states
– Therefore, the energy of the electron was proportional to the
distance the orbit was from the nucleus.

• Electrons emit radiation when they “jump” from an orbit

with higher energy down to an orbit with lower energy.
– The emitted radiation was a photon of light.
– The distance between the orbits determined the energy of
the photon of light produced.

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 Bohr Model of H Atoms

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The Nature of Energy
The energy absorbed or emitted
from the process of electron
promotion or demotion can be
calculated by the equation:
1 1
E = −hcRH ( nf2
- 2
ni )
where RH is the Rydberg
constant, 1.097  107 m−1, and ni
and nf are the initial and final
energy levels of the electron.
Electronic
Structure
of Atoms
© 2012 Pearson Education, Inc.
The Wave Nature of Matter
• Louis de Broglie posited
that if light can have
material properties,
matter should exhibit
wave properties.
• He demonstrated that the
relationship between
mass and wavelength
was
h
 = mv Electronic
Structure
of Atoms
© 2012 Pearson Education, Inc.
 Wave Behavior of Electrons

• De Broglie proposed that particles could have wave-like

character.

• De Broglie predicted that the wavelength of a particle was

inversely proportional to its momentum.

• Because it is so small, the wave character of electrons is

significant.

• De Broglie’s relation: h
𝜆=
mv

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 Problem Solving Using De Broglie’s
Relation
Example de Broglie Wavelength
What is the wavelength (in m) of an electron moving at 6.1 × 10 6 m/s (about 2% of c).
[Note that the length of a chemical bond is about 1.2 × 10 –10 m]

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 Electron Diffraction

• If electrons behave only like particles, there should be only

two bright spots on the target.

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 Electron Diffraction

Proof that the electron had wave nature came a few years
later with the demonstration that a beam of electrons would
produce an interference pattern the same as waves do.

However, electrons
actually present an
interference pattern,
demonstrating they
behave like waves.

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 An Electron’s Complementary Properties:
The Concept of Wave Duality and
Uncertainty
• An electron’s behavioral characteristics can be described
as follows:
– From a particulate perspective (e.g., matter, mass)
• Particle nature = position
– From an energy perspective (e.g., wavelength, frequency)
• Wave nature = interference pattern
– Problem: cannot observe both properties simultaneously
• The wave and particle nature of the electron are
complementary properties.
– The more you know about one, the less you know about
the other.

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 Heisenberg’s Uncertainty Principle

• Heisenberg stated that the product of the uncertainties in

both the position and speed of a particle was inversely
proportional to its mass.
– x = position, Δx = uncertainty in position
– v = velocity, Δv = uncertainty in velocity
– m = mass

Δx × mΔv > h/4 π

• This means that the more accurately you know the

position of a small particle, such as an electron, the less
you know about its speed, and vice versa.

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 Determinacy versus Indeterminacy

• According to classical physics, particles move in a path

determined by the particle’s velocity, position, and forces
acting on it.
– Determinacy = definite, predictable future

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 Determinacy versus Indeterminacy

• Because we cannot know both the position and velocity

of an electron, we cannot predict the path it will follow.
– Indeterminacy = indefinite future, can only predict probability

• The best we can do is to describe the probability an

electron will be found in a particular region using statistical
functions.

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 Indeterminacy Behavior of Electrons
• Electron behavior is indeterminate.
– Meaning, the path of an electron cannot be determined by its
position and velocity.
• Electron energy and position are complementary.
– KE = ½mv2
• For an electron with a given energy, the best we can do is describe a
region in the atom of high probability of finding it.
• Many of the properties of atoms are related to the energies of the
electrons.

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 Schrödinger’s Equation: Hψ = Eψ

• Schrödinger’s equation allows us to calculate the

probability of finding an electron with a particular
amount of energy at a particular location in
the atom.

• Solutions to Schrödinger’s equation produce many

wave functions, ψ.

• A plot of distance versus ψ 2 represents an orbital,

a probability distribution map of a region where the
electron is likely to be found.
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 Quantum Numbers:
The Solutions from the Wave Function, ψ
• Calculations show that the size, shape, and orientation in space
of an orbital are determined to be three integer terms in the wave
function.
– Added to quantize the energy of the electron
• These integers (solutions) are called quantum numbers.
– There are four quantum numbers:
• Principal quantum number, n
– Energy level
• Angular momentum quantum number, l
From
– Orbital type
solutions of Ψ
• Magnetic quantum number, ml
– Position of orbital in an X-Y-Z plot
• Spin quantum number, ms
– Orientation of the spin of the electron
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 Principal Quantum Number, n:
The Energy Level
• It characterizes the energy of the electron in a
particular orbital.
– It is Bohr’s energy level.

• Values of n can be any whole number integer > 1.

• It determines the size (overall) and energy of an

orbital.
– The larger the value of n, the more energy the
orbital has.
– The larger the value of n, the larger the orbital.

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 Principal Quantum Number, n:
The Energy Level
• Energies are defined as being “negative.”
– An electron’s energy is lowered (made more negative) as
a result of its interaction with the nucleus of the atom.
• An electron would have E = 0 when it escapes
the atom.

– As n gets larger, the following occurs:

• The amount of energy between orbitals gets smaller.
• The energy of the orbital becomes greater (less negative).

En = –2.18 × 10–18 J (1/n2) where n = 1, 2, 3, ….

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 Principal Energy Levels in Hydrogen

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 Angular Momentum Quantum Number, l:
The Orbital Quantum Number
• The angular momentum quantum number (l) determines
the shape of the orbital.
• l can have integer values from 0 to (n – 1).
• Each l value is designated by a particular letter that
designates the shape of the orbital.
– s orbitals are spherical.
• Have l value of zero (0)
– p orbitals are like two balloons tied at the knots (dumbbell
shape).
• Have l value of one (1)
– d orbitals are mainly like a flat four-leaf clover.
• Have l value of two (2)
– f orbitals are mainly like eight balloons tied at the knots.
• Have l value of three (3)

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 Magnetic Quantum Number, ml: The
Position or Orientation Quantum Number
• The magnetic quantum number is an integer that
specifies the orientation of the orbital.
– The direction in space the orbital is aligned relative to
the other orbitals.

• Values are integers from −l to +l.

– Including zero
– Gives the number of orbitals of a particular shape
• When l = 2, the values of ml are −2, −1, 0, +1, +2, which
means there are five orbitals with l = 2.

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 Spin Quantum Number, ms

• In the 1920s, it was

discovered that two
electrons in the same
orbital do not have
exactly the same energy.
• The “spin” of an electron
describes its magnetic
field, which affects its
energy.
Electronic
Structure
of Atoms
© 2012 Pearson Education, Inc.
 Spin Quantum Number, ms

• This led to a fourth

quantum number, the
spin quantum number,
ms.
• The spin quantum
number has only 2
allowed values: +1/2
and −1/2.
Electronic
Structure
of Atoms
© 2012 Pearson Education, Inc.
 Spin Quantum Number, ms

• The spin quantum number describes the spin

behavior (i.e., angular momentum) of an electron
in an atomic orbital.
– It specifies the orientation of the electron in the orbital.
• All electron spins are equal in magnitude; differ only in
orientation

• The numerical values assigned are + ½ (spin up)

or – ½ (spin down),

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 Describing an Orbital

• Each set of n, l, and ml describes one orbital.

• Orbitals with the same value of n are in the

same principal energy level.
– Also called the principal shell

• Orbitals with the same values of n and l are

said to be in the same sublevel.
– Also called a subshell

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 Illustration of Energy Levels and Sublevels

The n = 2 principal energy

level contains two sublevels:

a. The l = 0: 2s sublevel with

one orbital with ml = 0

b. The l = 1: 2p sublevel with

three p orbitals with
ml = –1, 0, +1

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 Quantum Number Practice
Example 2.5 Quantum Numbers I
What are the quantum numbers and names (for example, 2s, 2p) of the orbitals in the n = 4 principal level?
How many n = 4 orbitals exist?

Solution
First determine the possible values of l (from the given value of n). Then determine the possible values of ml for
each possible value of l. For a given value of n, the possible values of l are 0, 1, 2,..., (n – 1).

n = 4; therefore l = 0, 1, 2, and 3

For a given value of l, the possible values of ml are the integer values including zero ranging from –l to +l. The
name of an orbital is its principal quantum number (n) followed by the letter corresponding to the value l. The total
number of orbitals is given by n2.

For Practice 2.5

List the quantum numbers associated with all of the 5d orbitals. How many 5d orbitals exist?

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 Energy Levels and Sublevels

• In general, the following are true:

– The number of sublevels within a level = n.

– The number of orbitals within a sublevel = 2l + 1.

– The number of orbitals in a level = n2.

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 How Does the Quantum Mechanical Model
of an Atom Explain Atomic Spectra?
• Each wavelength in the spectrum of an atom
corresponds to an electron transition between orbitals.
• When an electron is excited, it transitions from an
orbital in a lower energy level to an orbital in a higher
energy level.
• When an electron relaxes, it transitions from an
orbital in a higher energy level to an orbital in a lower
energy level.
• When an electron relaxes, a photon of light is released
whose energy equals the energy difference between
the orbitals.

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 Electron Transitions: Excitations &
Radiation
• To transition to a higher energy state, the electron must gain
the correct amount of energy corresponding to the
difference in energy between the final and initial states.
• Electrons in high energy states are unstable and tend to
lose energy and transition to lower energy states.
• Each line in the emission spectrum corresponds to the
difference in energy between two energy states.

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 It Predicts the Spectrum of Hydrogen

• The wavelengths of lines in the emission spectrum

of hydrogen can be predicted by calculating the
difference in energy between any two states.

• For an electron in energy state n, there are (n – 1)

energy states it can transition to. Therefore, it can
generate (n – 1) lines.

• Both the Bohr and quantum mechanical models

can predict these lines very accurately for a
1-electron system.
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 Energy Transitions in Hydrogen
• The energy of a photon released is equal to the
difference in energy between the two levels the
electron is jumping between.

• It can be calculated by subtracting the energy of

the initial state from the energy of the final state.

ΔEelectron = Efinal state − Einitial state

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 Hydrogen Energy Transitions and Radiation

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 Problem Solving: Determining Wavelength
from an Electron Transition
Example Wavelength of Light for a Transition in the
Hydrogen Atom
Determine the wavelength of the light absorbed when an electron in a hydrogen atom
makes a transition from an orbital in which n = 2 to an orbital in which n = 7.

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 Probability and Radial Distribution Functions
and the Shapes of Atomic Orbitals
• ψ2 is the probability density.
– It is the probability of finding an electron at a particular point in
space.
– The probability density—the area most likely to find
the atom’s electron decreases as you move away from
the nucleus
• The radial distribution function represents the total
probability at a certain distance from the nucleus.
– Maximum at most probable radius
• Nodes in the functions are where the probability drops to 0.

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 Probability Density Function

The probability density function represents the total

probability of finding an electron at a particular point
in space.

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 Radial Distribution Function
The radial distribution function
represents the total probability
of finding an electron within a thin
spherical shell at a distance r
from the nucleus.

The probability at a point decreases

with increasing distance from the
nucleus, but the volume of the
spherical shell increases.

The net result is a plot that indicates

that the most probable distance of
the electron in a 1s orbital of H is
52.9 pm.
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 An Illustration of 2s and 3s Atomic Orbitals

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 l = 0, the s Orbital

• Each principal energy level

has one s orbital.

• Lowest energy orbital in a

principal energy state

• Spherical shaped

• Number of nodes = (n – 1).

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 l = 1, p orbitals
• Each principal energy state above n = 1 has three
p orbitals.
– ml = −1, 0, +1

• Each of the three orbitals points along a different axis.

– px, py, pz

• The second lowest energy orbitals in a principal

energy state

• Two-lobed

• One node at the nucleus; total of n nodes

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 Illustration of the Three Types of p Orbitals

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 l = 2, d Orbitals
• Each principal energy state above n = 2 has five d orbitals.
– ml = −2, −1, 0, +1, +2

• Four of the five orbitals are aligned in a different plane.

– The fifth is aligned with the z axis, dz squared.
– dxy, dyz, dxz, dx squared – y squared

• d orbitals:
– Mainly four-lobed “shaped” orbitals
– One has a two-lobed orbital with a ring/collar (toroid).

• Planar nodes
– Higher principal levels also have spherical nodes.
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 Illustration of the Five Types of d Orbitals

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 l = 3, f Orbitals

• Each principal energy state above n = 3 has seven

f orbitals.
– ml = −3, −2, −1, 0, +1, +2, +3

• f orbitals:
– Mainly eight-lobed
– Some have a two-lobed orbital with a ring/collar (toroid).

• Planar nodes
– Higher principal levels also have spherical nodes.

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 Illustration of the Seven Types of f Orbitals

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 The Phase of an Orbital
• Orbitals are determined from mathematical wave functions.
• A wave function can have positive or negative values.
– As well as nodes where the wave function = 0
• The sign of the wave function is called its phase.
• When orbitals interact, their wave functions may be in phase
(same sign) or out of phase (opposite signs).

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