Quantum Theory and Atomic Structure Second Semester - First Lesson

Explaining the Spectacular The light from neon signs and TV screens, as well as breathtaking firework and
aurora displays, occur through changes in atomic energy levels, which you'll examine in this chapter.

1. The Nature of Light

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1.1 The Wave Nature of Light

The wave properties of electromagnetic radiation are described by two interdependent variables.

Frequency (ν, Greek nu): is the number of cycles the wave undergoes per second and is expressed in
−1
units of 1/second [̄𝑠 ; also called hertz (Hz)].
Wavelength (λ, Greek lambda): is the distance between any point on a wave and the corresponding point
on the next crest (or trough) of the wave, that is, the distance the wave
travels during one cycle. Wavelength is expressed in meters and often, for
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very short wavelengths, in nanometers (nm, 10 m), picometers (pm,
−12 −10
10 m), or the non-SI unit angstroms (Å, 10 m).

Note that as the wavelength decreases, the frequency increases, and vise-versa.

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Light behaves like a wave, similar to how waves move on water. It has two important characteristics:

1. Wavelength (λ)
2. Frequency (ν)

Let’s relate these two properties to something you see every day, like waves at the beach and beats in
music.

Wavelength (λ): The Distance Between Waves

Imagine you are standing on the shore of a beach, watching waves roll in. The wavelength is the distance
between two wave crests — the high points of the waves. It can also be measured from one wave trough
(low point) to the next trough.

For light waves:

● Short wavelength means the waves are close together.

● Long wavelength means the waves are farther apart.

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Quantum Theory and Atomic Structure Second Semester - First Lesson

Real-Life Example: Colors of Light

Different colors of light have different wavelengths:

● Blue light has a short wavelength (waves are close together).

● Red light has a long wavelength (waves are farther apart).

➔ Frequency (ν): How Many Waves Pass in One Second

Now, imagine you’re counting how many waves hit the shore in one second. That’s the frequency — the
number of wave cycles passing a point per second.

For light waves:

● High frequency means more waves hit in one second.

● Low frequency means fewer waves hit in one second.

Real-Life Example: Types of Electromagnetic Waves

● Gamma rays have a high frequency (many waves per second).

● Radio waves have a low frequency (fewer waves per second).

Connecting Wavelength and Frequency

Wavelength and frequency are related — as one increases, the other decreases. Think of it like this:

● Short wavelength → High frequency (fast, rapid waves).

● Long wavelength → Low frequency (slow, gentle waves).

This relationship is why blue light (short wavelength) has more energy than red light (long wavelength).

Quick Recap Table

Term Real-Life Analogy Description

Wavelength (λ) Distance between ocean wave Distance from one wave crest to the next

Frequency (ν) Beats in a song How many waves pass a point in one second

Short Wavelength Fast, energetic waves Waves are close together

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Quantum Theory and Atomic Structure Second Semester - First Lesson

Long Wavelength Slow, calm waves Waves are farther apart

This connection between wavelength and frequency explains why different types of electromagnetic waves,
from radio waves to gamma rays, behave differently.

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The speed of the wave, the distance traveled per unit time (in units of meters per second), is the product of its
frequency (cycles per second) and its wavelength (meters per cycle):

𝑐𝑦𝑐𝑙𝑒𝑠 𝑚
Units for speed of wave: 𝑠
𝑥 𝑐𝑦𝑐𝑙𝑒
= 𝑚/𝑠

In a vacuum, all types of electromagnetic radiation travel at 2.99792458 ×

−8 −8
10 m/s (3.00 × 10 m/s to three significant figures), which is a physical
constant called the speed of light (c):

c=vxλ

Radiation with a high frequency has a short wavelength, and vice versa

FIGURE 7.2 Amplitude (intensity) of a wave. Amplitude is represented by the height of the crest (or depth of
the trough) of the wave. The two waves shown have the same wavelength (color) but different amplitudes and,
therefore, different brightnesses (intensities)

2. The Electromagnetic Spectrum

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FIGURE 7.3 Regions of the electromagnetic spectrum. The electromagnetic spectrum extends from the
very short wavelengths (very high frequencies) of gamma rays through the very long wave- lengths (very low
frequencies) of radio waves. The relatively narrow visible region is expanded (and the scale made linear) to
show the component colors.

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Quantum Theory and Atomic Structure Second Semester - First Lesson

● All the waves in the spectrum travel at the same speed through a vacuum but differ in frequency
and, therefore, wavelength
● Light of a single wavelength is called monochromatic (Greek, “one color”), whereas light of many
wavelengths is polychromatic.

3. The Classical Distinction Between Energy and Matter

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FIGURE 7.4 Different behaviors of waves and particles.
A. A wave passing from air into water is refracted (bent at
an angle).
B. In contrast, a particle of matter (such as a pebble)
entering a pond moves in a curved path, because
gravity and the greater resistance (drag) of the water
slow it down gradually.
C. A wave is diffracted through a small opening, which
gives rise to a circular wave on the other side. (The
lines represent the crests of water waves as seen from
above.)
D. In contrast, when a collection of moving particles
encounters a small opening, as when a handful of sand
is thrown at a hole in a fence, some particles move
through the opening and continue along their individual
paths.

4. The Particle Nature of Light

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(1) Blackbody radiation
(2) The photoelectric effect
(3) Atomic spectra

4.4 Max Planck

E = nhv
where:
● E is the energy of the radiation,
● ν is its frequency,
● n is a positive integer (1, 2, 3, and so on) called a quantum number, and
● h is a proportionality constant now known very precisely and called Planck’s constant
−34
(6.626 × 10 J•s)

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Quantum Theory and Atomic Structure Second Semester - First Lesson

An atom can emit only certain quantities of energy. The atom itself can have only certain quantities of
energy.

Thus, the energy of an atom is quantized: it exists only in certain fixed quantities, rather than being
continuous.

- energy packet is called a quantum (“fixed quantity”; plural, quanta), and its energy is equal to hν.

Thus, an atom changes its energy state by emitting (or absorbing) one or more quanta, and the energy of the
emitted (or absorbed) radiation is equal to the difference in the atom’s energy states:

∆𝐸𝑎𝑡𝑜𝑚 = 𝐸𝑒𝑚𝑖𝑡𝑡𝑒𝑑 (𝑜𝑟 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑) 𝑟𝑎𝑑𝑖𝑎𝑡𝑖𝑜𝑛 = ∆𝑛ℎ𝑣

∆𝐸 = ℎ𝑣

4.5 Albert Einstein

Albert Einstein proposed that light itself is particulate, that is, quantized into small “bundles” of
electromagnetic energy, which were later called photons.

Energy: fixed quantity and discrete particles

4.6 Atomic Spectra

FIGURE 7.7 The line spectra of several elements.
A. A sample of gaseous H₂ is dissociated into atoms and excited by an electric discharge. The emitted
light passes through a slit and a prism, which disperses the light into individual wave-lengths. The
line spectrum of atomic H is shown (top).
B. The continuous spectrum of white light is compared with the line spectra of mercury and strontium.
Note that each line spectrum is different from the others.

★ Animation: Atomic Line Spectra

★ Animation: Emission Spectra

FIGURE 7.8 Three series of spectral lines of atomic hydrogen. These series appear in different regions
of the electro- magnetic spectrum. The hydrogen spec- trum shown in Figure 7.7A is the visible series.

5. The Bohr Model of the Hydrogen Atom

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Quantum Theory and Atomic Structure Second Semester - First Lesson

Niels Bohr (1885–1962)

1. The H atom has only certain allowable energy levels, which Bohr called stationary states. Each of these
states is associated with a fixed circular orbit of the electron around the nucleus.
2. The atom does not radiate energy while in one of its stationary states.That is, even though it violates the
ideas of classical physics, the atom does not change energy while the electron moves within an orbit.
3. The atom changes to another stationary state (the electron moves to another orbit) only by absorbing or
emitting a photon whose energy equals the difference in energy between the two states:

𝐸𝑝ℎ𝑜𝑡𝑜𝑛 = 𝐸𝑠𝑡𝑎𝑡𝑒 𝐴 − 𝐸𝑠𝑡𝑎𝑡𝑒 𝐵 = ℎ𝑣

● In Bohr’s model, the quantum number n (1, 2, 3, . . .) is associated with the radius of an electron orbit,
which is directly related to the electron’s energy: the lower the n value, the smaller the radius of the
orbit, and the lower the energy level.

● When the electron is in the first orbit (n = 1), the orbit closest to the nucleus, the H atom is in its lowest
(first) energy level, called the ground state. If the H atom absorbs a photon whose energy equals the
difference between the first and second energy levels, the electron moves to the second orbit (n = 2),
the next orbit out from the nucleus. When the electron is in the second or any higher orbit, the atom is
said to be in an excited state.

FIGURE 7.9 Quantum staircase. In this analogy for the energy levels of the hy- drogen atom, an electron can
absorb a photon and jump up to a higher "step" (stationary state) or emit a photon and jump down to a lower
one. But the elec- tron cannot lie between two steps.

FIGURE 7.10 The Bohr explanation of three series of spectral lines.

A. According to the Bohr model, when an electron drops from an outer orbit to an inner one, the atom
emits a photon of specific energy that gives rise to a spectral line. In a given spectral series, each
electron drop has the same inner orbit, that is, the same value of n, in the Ryd- berg equation (see
2
Equation 7.3). (The orbit radius is proportional to 𝑛 . Only the first six orbits are shown.)

B. An energy diagram shows how the ultraviolet series arises. Within each series, the greater the
difference in orbit radil, the greater the difference in energy levels (depicted as a downward arrow),
and the higher the energy of the photon emitted. For example, in the ultraviolet series, in which 𝑛1=
1 a drop from 5 to n = 1 from emits a photon with more energy (shorter λ, higher 𝑣) than a drop from
n = 2 to n = 1 [The axis shows negative values because n = ∞(the electron completely separated
from the nucleus) is defined as the atom with zero energy]

As a picture of the atom, the Bohr model is incorrect, but we still use the terms “ground state” and “excited
state” and retain one of Bohr’s central ideas in our current model:

the energy of an atom occurs in discrete levels

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Quantum Theory and Atomic Structure Second Semester - First Lesson

6. The Wave-Particle Duality of Matter and Energy

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The early proponents of quantum theory demonstrated that energy is particlelike. Physicists who developed
the theory turned this proposition upside down and showed that matter is wavelike.

6.7 The Wave Nature of Electrons and the Particle Nature of Photons
Louis de Broglie:
if energy is particle-like, perhaps matter is wavelike.
ℎ
λ = 𝑚𝑢

FIGURE 7.12 Wave motion in restricted systems.

A. In a musical analogy to electron waves, one half-wavelength (λ / 2) is the "quantum" of the guitar
string's vibration. The string length L is fixed, so the only allowed vibrations occur when L is a
whole-number multiple (n) of λ/ 2
B. If an electron occupies a circular orbit, only whole numbers of wavelengths are allowed ( n = 3 and
1
n = 5 are shown). A wave with a fractional number of wave- lengths (such as n = 3 3
) is "forbidden"
because it rapidly dies out through overlap of crests and troughs.

★ Standing Waves Demo

Table 7.1 The De Broyle Wavelengths (λ)

7. The Heisenberg Uncertainty Principle

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In the classical view of the world, a moving particle has a definite location at any instant, whereas a wave is
spread out in space. If an electron has the properties of both a particle and a wave, what can we determine
about its position in the atom?

Werner Heisenberg
In 1927, the German physicist Werner Heisenberg postulated the uncertainty principle, which states that it
is impossible to know the exact position and momentum (mass times speed) of a particle simultaneously.

We cannot assign fixed paths for electrons, such as the circular orbits of Bohr’s model.

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Quantum Theory and Atomic Structure Second Semester - First Lesson

The most we can ever hope to know is the probability—the odds—of finding an electron in a given region of
space; but we are not sure it is there any more than a gambler is sure of the next roll of the dice.

8. The Quantum-Mechanical Model of the Atom

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Quantum mechanics - examines the wave nature of objects on the atomic scale.

Erwin Schödinger
In 1926, Erwin Schrödinger derived an equation that is the basis for the quantum-mechanical model of the
hydrogen atom. The model describes an atom that has certain allowed quantities of energy due to the allowed
frequencies of an electron whose behavior is wavelike and whose exact location is impossible to know.

8.9 Atomic Orbital

It’s important to keep in mind that an “orbital” in the quantum-mechanical model bears no resemblance to
an “orbit” in the Bohr model: an orbit was, supposedly, an electron’s path around the nucleus, whereas an
orbital is a mathematical function with no direct physical meaning.

8.10 Probability Density

A measure of the probability that the electron can be found within a particular tiny volume of the atom.

For a given energy level, we can depict this probability with an electron probability density diagram, or
more simply, an electron density diagram/electron cloud.

FIGURE 7.15 Electron probability density in the ground-state H atom.

A. An electron density diagram shows a cross section of the H atom. The dots, each representing the
probability of the electron being within a tiny volume, decrease along a line outward from the
nucleus.
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B. A plot of the data in A shows that the probability density (ψ ) decreases with distance from the
nucleus but does not reach zero (the thickness of the line makes it appear to do so).
C. Dividing the atom's volume into thin, concentric, spherical layers (shown in cross section) and
counting the dots within each layer gives the total probability of finding the electron within that layer.
D. A radial probability distribution plot shows total electron density in each spherical layer vs. 𝑟.
Because electron density decreases more slowly than the volume of each con- centric layer
increases, the plot shows a peak.
E. A 90% probability contour shows the ground state of the H atom (orbital of lowest en- ergy) and
represents the volume in which the electron spends 90% of its time

9. Quantum Numbers of an Atomic Orbital

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Quantum Theory and Atomic Structure Second Semester - First Lesson

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An atomic orbital is specified by three quantum numbers. One is related to the orbital’s size, another to its
shape, and the third to its orientation in space.

1. The principal quantum number (n) is a positive integer (1, 2, 3, and so forth).
➔ It indicates the relative size of the orbital. The principal quantum number specifies the energy level
of the H atom: the higher the n value, the higher the energy level. When the electron occupies an
orbital with n = 1, the H atom is in its ground state and has lower energy than when the electron
occupies the n = 2 orbital (first excited state).

2. The angular momentum quantum number (l) is an integer from 0 to n - 1.

➔ It is related to the shape of the orbital and is sometimes called the orbital-shape (or azimuthal)
quantum number. Note that the principal quantum number sets a limit on the values for the angular
momentum quantum number; that is, n limits l. For an orbital with n = 1, l can have a value of only 0.
For orbitals with n = 2, l can have a value of 0 or 1; for those with n = 3, l can be 0, 1, or 2; and so forth.
Note that the number of possible l values equals the value of n.

3. The magnetic quantum number (ml) is an integer from -1 through 0 to +1.

➔ It prescribes the orientation of the orbital in the space around the nucleus and is sometimes called
the orbital-orientation quantum number. The possible values of an orbital’s magnetic quantum number
are set by its angular momentum quantum number; that is, l sets the possible values of 𝑚𝑙. An orbital
with l = 0 can have only ml = 0. However, an orbital with l = 1 can have any one of three ml values, -1,
0, or +1; thus, there are three possible orbitals with l = 1, each with its own orientation. Note that the
number of possible ml values equals the number of orbitals, which is 2/ + 1 for a given l value.

Table 7.2 The Hierarchy of Quantum Numbers for Atomic Orbitals

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1. Level: The atom’s energy levels, or shells, are given by the n value: the smaller the n value, the lower the
energy level and the greater the probability of the electron being closer to the nucleus.
2. Sublevel: The atom’s levels contain sublevels, or subshells, which designate the orbital shape. Each
sublevel has a letter designation:

l = 0 is an s sublevel.
l = 1 is a p sublevel.
l = 2 is a d sublevel.
l = 3 is an f sublevel.

sharp, principal, diffuse, and fundamental

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Quantum Theory and Atomic Structure Second Semester - First Lesson

3. Orbital: Each allowed combination of n, l, and ml values specifies one of the atom’s orbitals. Thus, the three
quantum numbers that describe an orbital express its size (energy), shape, and spatial orientation.
You can easily give the quantum numbers of the orbitals in any sublevel if you know the sublevel
letter designation and the quantum number hierarchy. For example, the 2s sublevel has only one
orbital, and its quantum numbers are n = 2, l = 0, and ml = 0. The 3p sublevel has three orbitals:
one with n = 3, l = 1, and ml = 1; another with n = 3, l = 1, and 𝑚𝑙 = 0; and a third with n = 3, l = 1,
and 𝑚𝑙 = 1.

FIGURE 7.17 The 2p orbitals.

A. A radial probability distribution plot of the 2p orbital shows a sin- gle peak. It lies at nearly the same
distance from the nucleus as the larger peak in the 2s plot (shown in Figure 7.16B),
B. A cross section shows an electron cloud representation of the 90% probability contour of the 2𝑝𝑧,
orbital. An electron occupies both regions of a 2p orbital equally and spends 90% of its time within
this volume. Note the nodal plane at the nucleus.
C. An accurate rep- resentation of the 2𝑝𝑧 probability contour. The 2𝑝𝑥 and 2𝑝𝑦 orbitals lie along the x
and y axes, respectively.
D. The stylized depiction of the 2p probability contour used throughout the text.
E. In an atom, the three 2p orbitals occupy mutually perpendicular regions of space, contributing to the
atom's overall spherical shape

FIGURE 7.18 The 3d orbitals.

A. A radial probability distribution plot.
B. An electron cloud repre sentation of the 3𝑑𝑦𝑧 pr orbital in cross section. Note the mutually
perpendicular nodal planes and the lobes lying between the axes.
C. An accurate representation of the 3𝑑𝑦𝑧 orbital probability contour.
D. The stylized depiction of the 3𝑑𝑦𝑧 orbital used throughout the text.
E. The 3𝑑𝑥𝑧 orbital,
F. The 3𝑑𝑥𝑦 orbital.
G. The lobes of the 3𝑑 2 2 orbital lie on the x and y axes.
𝑥 −𝑦
H. The 3𝑑 2 orbital has two lobes and a central, donut-shaped region.
𝑧
I. A composite of the five 3d orbitals, which again contributes to an atom's overall spherical shape.

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