Chapter 8

The Quantum-Mechanical Model of the Atom

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 Part 8.1: Schrödinger’s Cat
• Subatomic particles are so small we can not accurately describe them using classical
mechanics/physics.

• Rather, we must use a quantum mechanical model, one that was developed by
physicists (Albert Einstein, Niels Bohr, Louis de Broglie, Max Planck, Werner Heisenberg,
P. A. M. Dirac, and Erwin Schrödinger) in the early 20th century.

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 Part 8.2: The Nature of Light

Slide #4: The Wave Nature of Light

Slide #5: Characteristics of a Wave – Amplitude, Wavelength, and Frequency
Slide #6: The Electromagnetic (EM) Spectrum
Slide #7: The Electromagnetic (EM) Spectrum (cont.) – Gamma, x-ray, and UV waves
Slide #8: The Electromagnetic (EM) Spectrum (cont.) – Visible and IR radiation
Slide #9: The Electromagnetic (EM) Spectrum (cont.) – Microwaves & Radio waves
Slide #10: Interference and Diffraction of Light Waves
Slide #11: Diffraction – Double Slit Experiment
Slide #12: The Particle Nature of Light and the Photoelectric Effect

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 The Wave Nature of Light
• Light is a type of energy. It is electromagnetic radiation that consists of oscillating electric
and magnetic fields that are perpendicular to each other.

• Light travels at incredibly fast speeds. In a vacuum light travels at 3.00 x 108 m/s (or
186,000 mi/s).

• Light travels roughly a million times faster than sound. So, you see a lightning bolt almost
instantaneously, but the sound of the thunder that accompanies it takes much longer to
reach your ear. There is a five second delay in the sound wave for each mile between you
and the lightning bolt.

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 Characteristics of a Wave – Amplitude, Wavelength, and Frequency
• The amplitude of a wave is the vertical height of a crest (or depth of a trough).

• The wavelength (λ) of a wave is the distance between adjacent crests.

• The frequency (ν) of a wave is the number of waves that pass through a stationary
point in each period (e.g., per second).

• Wavelength and frequency are inversely

related. Their product equals a constant,
c, the speed of light:

c = νλ
or
ν=
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 The Electromagnetic (EM) Spectrum
High energy Low energy

ultra-
violet red infrared
violet

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 The Electromagnetic (EM) Spectrum (cont.)
• Gamma(γ) rays: the highest energy (and frequency), shortest wavelength EM radiation.
Exposure results in extensive damage to biological molecules. Used is kill
cancer cells.

• X-rays: the second most energetic EM radiation. Used to image bones and
teeth because it passes through soft issue.

• Ultraviolet (UV): The source of sunburn. Excessive exposure can result in skin cancer and
cataracts. Subdivided into UV-A, UV-B, and UV-C:

 UV-A (315-400 nm): black light, not absorbed by

stratospheric ozone layer.
 UV-B (280-315 nm): mostly absorbed by ozone layer
stratospheric ozone layer.
 UV-C (100-280 nm): completely absorbed by
stratospheric ozone layer. 7
 The Electromagnetic (EM) Spectrum (cont.)
• Visible (380-750 nm): the portion of the EM spectrum visible to the human eye. Violet
light, the highest energy (frequency) visible light, borders the ultraviolet (UV) region.
Red light the lowest energy (frequency) visible light, borders the infrared (IR) region.

UV IR

• Infrared (IR): this radiation is associated with the heat you feel when you are near hot
objects. All warm objects, humans included emit infrared light. This is the basis of
night vision technology.

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 The Electromagnetic (EM) Spectrum (cont.)

• Microwaves (1mm – 1 m): is the radiation used in microwave ovens. These waves are
energetic enough to cause polar water to rotate and produce thermal energy. Heating
a nonpolar liquid (e.g., CS2) does not cause it to heat up.

• Radio waves: cover a range from 300 gigahertz (GHz) to 30 hertz (Hz). A 300 GHz wave has
a wavelength of 1 millimeter (1 mm) and a 30 Hz wave has a wavelength of 10,000 km or
6,214 miles. Radio waves are generated by charged particles undergoing acceleration.
They are generated by a transmitter and detected by a receiver.

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 Interference and Diffraction of Light Waves
• Constructive interference occurs when two waves are in phase when they interact.
If the two waves are of the same amplitude a wave of twice the amplitude results.
• Destructive interference occurs when two waves are totally out of phase when they
interact. If the two waves are of the same amplitude the two waves cancel each other
out.

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 Diffraction – Double Slit Experiment
• Diffraction occurs when light passes through an opening or aperture. The resulting wave
depends on the size of the slit compared to the wavelength of the light – see below. This
is a single slit experiment.

• In a double slit experiment, a series of bright and dark lines appear on a screen – see below.

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 The Particle Nature of Light and the Photoelectric Effect
• The photoelectric effect describes the observation that many metals emit electrons when light with a
sufficiently high energy shines on them.
• Classical EM theory predicted:
 Only the amplitude of the light wave and not its wavelength affected the rate of electron ejection.
 Dim light would result in a lag time between the arrival of the incident light and the ejection of an
electron. More intense light would decrease the lag time.
• The results from the experimental observation of the photoelectric effect showed that there was a
threshold frequency. Lower energy (frequency) light did not reject any electrons.

• In 1905 Albert Einstein explained the photoelectric effect by suggesting that light is quantized, that is, it
comes in packets called photons. The energy of a photon is: E = hν, where h = 6.626 x 10–34 J∙s and is
labeled Planck's constant. The energy of a photon is also equal to . This led to the label: the wave-
particle duality of light.
• The binding energy of an emitted electron, ϕ, is equal to the energy of the photon, hν. Until the energy of
the photon is ≥ the energy of the electron, ϕ, no electrons are rejected.
• The kinetic energy (KE) of the ejected electron is the difference between the energy of the photon (hν)
and the binding energy of the electron:
KE = hν - ϕ
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 Part 8.3: Atomic Spectroscopy and the Bohr Model

Slide #14: Emission Spectra and the Bohr Model

Slide #15: Different Series of Lines for the H Atom – Emission Spectra of H
Slide #16: The Bohr Model

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 Emission Spectra and the Bohr Model
• When an atom absorbs energy (heat, light, electricity) it often reemits energy in the form
of light. These spectra are labeled emission spectra. These emission spectra exhibit the
following attributes:
 They are line spectra and not a continuous spectra.
 For a given element the emission spectra is always the same.
 Each element exhibits a unique line spectrum unlike any other element.
• Johannes Rydberg developed an empirical expression the predicts the line emission
spectrum of hydrogen. However, this expression didn’t explain why atoms behave this
way.
• Niels Bohr developed a model of the H atom to explain its atomic emission spectrum. His
assumptions included:
 The electrons travel in circular orbits around a small dense nucleus.
 These orbits only occurred at a fixed energy. They were quantized.
 Absorption or emission energy only occurred when an electron moved from one orbit
to another. 14
 Different Series of Lines for the H Atom – Emission Spectra of H
• Note:
 Lines for the Lyman series all appear in the
UV region of the EM spectrum.
 Lines for the Balmer series all appear in the
visible region of the EM spectrum.
 Lines for the Paschen series all appear in the
infrared (IR) region of the EM spectrum.

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 Part 8.4: The Wave Nature of Matter: The de Broglie
Wavelength, the Uncertainty Principle, and Indeterminacy

Slide #18: The de Broglie Wavelength and Heisenberg Uncertainty Principle

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The de Broglie Wavelength and Heisenberg Uncertainty Principle
• The wavelength (λ) of an electron of mass m moving at velocity v is given by the de Broglie relation,
where h equals Planck’s constant:
λ=
• The wave nature and particle nature of an electron are complementary properties. The more we know
about one, the less we know about the other.

• This idea was formalized by the Heisenberg Uncertainty Principle:

(Δx)(mΔv) ≥
where Δx is the uncertainty in the position and Δv is the uncertainty in the velocity.

• For large objects that move slowly (e.g., a baseball or cannon ball), both the position and velocity can
be measured allowing us to predict the ball’s trajectory. Newton’s laws apply here, and we have
deterministic behavior.
• For extremely small objects that move incredibly fast (e.g., an electron), neither the position nor the
velocity can be precisely defined. Newton’s laws do not apply here and the best we can do is generate
a probability distribution map of the trajectory of the electron. Here we rely on quantum mechanics.
The electron exhibits indeterministic behavior.
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 Part 8.5: Quantum Mechanics and the Atom

Slide #20: The Schrödinger Equation, Hψ = Eψ

Slide #21: The Four Quantum Numbers
Slide #22: Quantum Numbers (cont.)
Slide #23: More Information About the Four Quantum Numbers
Slide #24: Shells, Subshells, and Orbitals
Slide #25: Subshells
Slide #26: The Interrelationships Between the First Three Quantum
Numbers, n, ℓ , and mℓ
Slide #27: Summary Statements About the Four Quantum Numbers

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 The Schrödinger Equation, Hψ = Eψ
• The Schrödinger equation, Hψ = Eψ, can be solved exactly for the H atom, which contains
one proton and one electron. This is not the case for larger atoms, however.

• Because position and velocity are indeterminant qualities in the case of the electron, and
because energy is related to velocity by the expression KE = ½mv2, it follows that energy
and position are indeterminant qualities as well.

• If for the electron, we define its energy precisely, then as regards its position the best we
can do is provide a probability distribution map of its location called an orbital.

• The solution to the Schrödinger equation for the H atom yields multiple solutions (called
wave functions which are mathematically complex). At this level, we bypass this
information and examine graphical representations of the orbitals.

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 The Four Quantum Numbers
• Each orbital comes with three interrelated quantum numbers:

 The principal quantum number, n.

 The angular momentum quantum number, ℓ.

 The magnetic quantum number, mℓ.

• A 4th quantum number is added called the spin quantum number, ms, which
communicates whether the spin of the electron is clockwise (CW) or counterclockwise
(CCW). This is a classical mechanical interpretation of the behavior of the electron
and not a quantum mechanical interpretation. Think of a spinning top. It can either
spin CW or CCW.

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 Quantum Numbers (cont.)
• The first three quantum numbers are interrelated. They are assigned integer values.
 The value of n limits the possible values of ℓ.
 In turn, the value of ℓ limits the possible values of mℓ.

• The principal quantum number, n, communicates the size and energy of an orbital. Its
possible values are n = 1, 2, 3, 4, … .

 Since n = is assigned an energy of zero, the lower

energy states have a negative value.
 The n = 1 energy state is called the ground state.
 The spacing between energy states gets smaller as
n increases.
Energy levels for the H atom.
1 eV = 1.602 x10-19 J
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 More Information About the Four Quantum Numbers (cont.)
• The angular momentum quantum number, ℓ, communicates the shape of the orbital.

• The possible values of ℓ are ℓ = 0, 1, 2, 3 … n – 1.

• The ℓ quantum number is often communicated by a lowercase letter:

• When n = 1, ℓ can only equal 0. The shorthand nℓ designation is 1s.

• When n = 2, ℓ can equal 0 and 1. The shorthand nℓ designations are 2s and 2p.

• When n = 3, ℓ can equal 0, 1 and 2. The shorthand nℓ designations are 3s, 3p and 3d.

• When n = 4, ℓ can equal 0, 1, 2 and 3. The shorthand nℓ designations are 4s, 4p, 4d & 4f.
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Shells, Subshells, and Orbitals

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 Subshells
• The magnetic quantum number, mℓ, communicates the orientation of the orbital in space.
The possible values of mℓ are -ℓ, …,0, …,+ℓ. This works out as follows:

 When ℓ = 0 (an s orbital), mℓ = 0.

 When ℓ = 1 (a p orbital), mℓ = -1, 0, +1.
 When ℓ = 2 (a d orbital), mℓ = -2, -1, 0, +1, +2.
 When ℓ = 3 (an f orbital), mℓ = -3, -2, -1, 0, +1, +2, +3.

• Orbitals with the same value of n are said to be in the same principal level or principal shell.
• Orbitals with the same value of n and ℓ are said to be in the same subshell.
• The number of orbitals in any subshell is equal to 2ℓ + 1.
• The number of orbitals in a shell is equal to n2. Therefore, there is/are:
 One orbital for n = 1, namely 1s.
 Four orbitals for n = 2, namely 2s, 2px, 2py, and 2pz.
 Nine orbitals for n = 3, namely 3s, 3px, 3py, 3pz, 3dxy, 3dxz, 3dyz, 3dx2-y2, and 3dz2. 25
The Interrelationships Between the First Three Quantum Numbers, n, ℓ , and mℓ

Shell n ℓ mℓ Degeneracy Designation n2

K 1 0 0 1 1s 1

L 2 0 0 1 2s 4
2 1 -1, 0, +1 3 2px, 2py, 2pz

3 0 0 1 3s
M 3 1 -1, 0, +1 3 3px, 3py, 3pz 9
3 2 -2, -1, 0, +1, +2 5 3dxy, 3dxz, etc.

4 0 0 1 4s
N 4 1 -1, 0, +1 3 4px, 4py, 4pz 16
4 2 -2, -1, 0, +1, +2 5 4dxy, 4dxz, etc.
4 3 -3, -2, -1, 0, +1, +2, +3 7 4fxyz, etc.

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Summary Statements About the Four Quantum Numbers

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 Part 8.6 The Shape of Atomic Orbitals

Slide #29: The s Orbital

Slide #30: Radical Distribution Functions (Plots) for the 1s, 2s, and 3s Orbitals
Slide #31: The p Orbitals
Slide #32: The d Orbitals
Slide #33: Radial Nodes for s, p, and d Orbitals

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 The s Orbital
• The lowest energy orbital is the spherically symmetric
1s orbital. Figure A is a dot representation of the electron
probability density for the 1s, 2s, and 3s orbitals.
A
• In Figure B, the orbital surface of the 1s, 2s, and 3s orbitals
is provided. These images are the wave function squared,
ψ2.

• Figure C is a cut-away of the 1s, 2s, and 3s orbitals.

Note: the presence of one node for the 2s orbital and two B
nodes for the 3s orbital. These nodes are called radial nodes
or spherical nodes. The number of radial nodes = n - ℓ - 1.

• A node is a region of space where the electron density is zero.

In three dimensions it is either a spherical shell or a plane. C
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Radical Distribution Functions (Plots) for the 1s, 2s, and 3s Orbitals

• A radial distribution function is a plot where the y-axis is electron probability (ψ2r2) vs.
distance from the nucleus, r, along the x-axis.
• Note three features of this plot:

 The maxima of the curves show the greatest

probability of finding an electron in an
orbital.
 As n increases from 1 to 2 to 3, the electron
density is concentrated further and
further away from the nucleus.
 The 1s orbital (purple) has zero radical nodes.
The 2s orbital (green) and has one radical node
and the 3s orbital (red) has two radial nodes.

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 The p Orbitals
• Pictured below are the 2px, 2py, and 2pz orbitals. Recall the quantum numbers for
the 2p orbitals are n = 2, ℓ = 1, and mℓ = -1, 0, and +1.
• These three orbitals are said to be triply degenerate. That is, they have the same shape
and the same energy. They differ only in their orientation in space as indicated by the
three values for mℓ.
• The p orbitals are said to be ungerade, which means they lack a center of symmetry.
One lobe is labeled (+) and the other (–).
• All p orbitals have a nodal plane. The formula for the number of nodal planes is ℓ.

– – +
+ +
–

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 The d Orbitals
• Pictured below are the 3d orbitals. Recall the quantum numbers for the 3d orbitals are
n = 3, ℓ = 2, and mℓ = -2, -1, 0, +1 and +2.
• These five orbitals are said to have a degeneracy of five. That is, they have the same shape
(except one) and the same energy. They differ only in their orientation in space as
indicated by the five values for mℓ.
• The d orbitals are said to be gerade, which means they possess a center of symmetry.
Two opposite lobes are labeled (+) and the other two (–). See the middle d orbital. The s
orbital is also gerade. The f orbitals are ungerade.
• All d orbitals have two nodal planes. The formula for the number of nodal planes is ℓ.

– +
+ –
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Radial Nodes for s, p, and d Orbitals

The number of radial nodes = n - ℓ - 1

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