Chapter 7 Notes

CHEM 1411 General Chemistry Chemistry: A Molecular Approach by Nivaldo J. Tro

The Quantum-
7 Mechanical Model
of the Atom
Chapter Objectives:
• Understand the relationship between wavelength,
frequency, and energy of light.
• Understand the origin of atomic line spectra.
• Learn how the quantum numbers are used to
understand the arrangement of electrons in atoms.
• Learn the atomic orbitals and their basic shapes.
Mr. Kevin A. Boudreaux
Angelo State University 1
www.angelo.edu/faculty/kboudrea

Quantum Mechanics: A Theory That Explains

the Behavior of the Absolutely Small
• The distribution of electrons in atoms is explained in
modern science using a branch of physics called
quantum mechanics, which describes the behavior
of things of extremely small things.
• Explaining the behavior of extremely small things,
like electrons in atoms (whose arrangement gives
rise to an element’s chemical properties) requires
completely different ideas from the way that we
model the behavior of larger objects.
• The quantum-mechanical model of the atom
explains why the periodic table has the form that it
does, and provides the basis of our understanding of
how chemical bonds form.
2
Chapter 7 Notes

The Wave Nature

of Light

A Brief History of Light

The Road to Quantum Mechanics is Paved with Good Intentions
• For many years, scientists debated about whether
light was best understood as a stream of particles or
as a wave phenomena.
– Robert Hooke (1665) — light is a wave.
– Isaac Newton (late 1600’s) — light is a stream of particles.
– Thomas Young (1801) — explained diffraction using the wave
theory of light.
– James Clerk Maxwell (1864) — developed a mathematical
description of EM radiation in terms of oscillating fields of electrical
and magnetic waves, known as Maxwell’s equations:
∫ E • dA = q / ε 0

∫ B • dA = 0
dΦ B
∫ E • ds = - dt
dΦ
∫ B • ds = μ0ε 0 dt E + μ0i 4
Chapter 7 Notes

Light and Matter

• We now know that both light and electrons exhibit
wave-particle duality — that is, some properties of
each are best described with a wave model, and
some properties are best described by a particle
model.
• Quantum mechanics, which unifies the wave and
particle models of light, arose from a combination of
the attempts by physicists and chemists to
understand both the structure of the atom, and their
attempts to understand the behavior of light.
• Many basic clues to the structure of atoms came
from the study of light. (This is because light is
ultimately emitted by matter).

Electromagnetic Radiation
• Visible light, infrared radiation, ultraviolet light,
radio waves, microwaves, X-rays, and gamma rays
are types of electromagnetic (EM) radiation,
which consist of energy propagated by electric and
magnetic fields that are perpendicular to each other,
and that alternately increase and decrease in
intensity as they move through space. (movie)

6
Figure 7.1
Chapter 7 Notes

Frequency, Wavelength, and Amplitude

• EM radiation traveling through a vacuum behaves in
some ways like ocean waves traveling through
water. The wave properties of EM radiation are
described by three variables:
– Wavelength (λ, lambda) — the distance from
one wave peak to the next (or from one wave
trough to the next) (units of length, m).
– Amplitude — the height of the wave, measured
from the center line between peak and trough; the
intensity or brightness of the light is proportional
to the square of the amplitude.
– Frequency (ν, nu) — the number of wave peaks
that pass by a given point per unit of time (units
of cycles per second, 1/second, s-1, Hz [Hertz]).
7

Frequency, Wavelength, and Amplitude

8
p. 283, Figure 7.2
Chapter 7 Notes

The Speed of Light; Relating ν and λ

• In a vacuum, all EM radiation travels at the same
speed: 2.99792458×108 m/s, known as c, the speed
of light.
• Because the speed of light is a constant, frequency
and wavelength are inversely proportional to each
other:
c = λ ν = 3.00×108 m s-1
• What’s different about each type of EM radiation is
its wavelength and frequency (and also the energy of
the radiation [later]).
• Visible light extends from wavelengths of 750 nm
(red) to 400 nm (violet); “white light” is a
combination of all of these wavelengths of radiation.
9

The Electromagnetic Spectrum

• The colors that we see around us results from an
object absorbing some wavelengths of visible
radiation and reflecting others back to our eyes.
• White light from the sun can be spread out with a
prism to form a continuous spectrum, with no
breaks in between the colors:

• Visible light represents only a small portion of the

continuum of radiant energy known as the
electromagnetic spectrum.
– Higher frequency light includes ultraviolet (UV)
rays, X-rays, and gamma rays.
– Lower frequency light includes infrared (IR)
radiation, microwaves, and radio waves. 10
Chapter 7 Notes

The Electromagnetic Spectrum

11
Figure 7.5

Examples: Frequency and Wavelength

1. A dental hygienist uses x-rays (λ = 1.00 Å [Å =
angstrom; 1 Å = 10-10 m) to take a series of dental
radiographs while the patient listens to a radio
station (λ = 325 cm) and looks out the window at the
blue sky (λ = 473 nm). What is the frequency (in s-
1) of the EM radiation from each source? (sim. to
For Practice 7.1)

Answer: 3.00×1018 s-1, 9.23×107 s-1, 6.34×1014 s-1 12

Chapter 7 Notes

Examples: Frequency and Wavelength

2. What is the wavelength (in nm) of yellow light with
a frequency of 5.22×1014 Hz? (sim to Ex. 7.1)

Answer: 575 nm 13

Constructive and Destructive Interference

• Waves can interfere with each other constructively
or destructively:

Wave amplitudes add Wave amplitudes cancel

Constructive interference Destructive interference 14
Chapter 7 Notes

Diffraction
• A wave bends around an object that is comparable in
size to its wavelength, producing a new set of waves
in a process called diffraction:

• A stream of particles, on the other hand, would

either be blocked by the barrrier, or sail through the
opening without being diffracted:

15
Figure 7.6

Diffraction
• If light strikes a barrier with two slits (with a
separation comparable to the wavelength of the
light), the light is diffracted through both slits,
producing an interference pattern on the other side.
This phenomena would be produced by anything
which has wave properties, but not by something
that has particle properties.

16
Figure 7.7
Chapter 7 Notes

The Particle Nature

of Light

17

Houston, We’ve Got A Problem

• By the mid-1800’s, with the development of
Maxwell’s equations, the nature of light seemed to
be well-understood, but in the late 19th and early 20th
centuries, three newly discovered phenomena
proved difficult to explain using the wave models of
classical mechanics:
1. blackbody radiation
2. the photoelectric effect
3. atomic line spectra
• Ultimately, an entirely new way of looking at energy
was required to understand these phenomena. This
explanation — quantum mechanics — also led to
our modern understanding of the structure of the
atom.
18
Chapter 7 Notes

Problem 1: Blackbody Radiation

• Blackbody radiation is the visible glow that solid
objects give off when heated, as a result of the
vibration of electrons within the solid (e.g., the
heating element of a metal stovetop, the hot metal
filament in a light bulb). [movie]
• When iron is heated, it first glows a dull red color,
becomes orange as the temperature increases, then a
blinding white glare, and eventually a dull blue.
– The longer wavelengths (red)
have a lower intensity, and the
shorter wavelengths (white, blue)
have a higher intensity.
– If this trend were to continue, the
intensity would be even higher in
the UV range; instead, the
intensity reaches a maximum,
and then falls off with shorter
wavelengths. 19
← decreasing wavelength

Solution: Walking the Planck

• Classical physics was unable to explain the variation
in radiation emitted at different temperatures.
• In 1900, Max Planck (Nobel Prize, 1918) concluded
that the energy radiated by a heated object can’t be
continuously variable; instead the energy is emitted
only in discrete amounts, or quanta (singular,
quantum). [Think stairs instead of ramps.]
• Each change in the energy of the atoms in a heated
substance results from the gain or loss of these
“packets” of energy. The amount of energy, E,
associated with each quantum of energy is given by
the Planck equation:
E = hν
h = Planck’s constant = 6.626×10-34 J s
20
Chapter 7 Notes

Problem 2: The Photoelectric Effect

• The photoelectric effect occurs when light shines
on a metal, causing it to emit electrons.
– The frequency of the light must be above some threshold
frequency, which is different for each metal, below which
no electrons are emitted, no matter how bright the light is.
– Low frequency light will not eject electrons from the
metal, no matter how bright the light or how long it
shines, but high frequency light will eject electrons, even
if the light is dim.

21
Figure 7.8 MOV: Photoelectric Effect

Solution: Einstein Saves the Day

• Albert Einstein (1905, Nobel Prize, 1921) explained
the photoelectric effect by proposing that light
behaves as if it were a stream of small, massless
packets of energy, called photons, having an energy
given by the Planck equation:
Ephoton = hν (or E = hc/λ)
h = Planck’s constant = 6.626×10-34 J s
• The energy of a photon of EM radiation is directly
proportional to its frequency (color, wavelength);
while the intensity (brightness) of the light is due to
the number of photons.
– When a low-energy (low ν) photon strikes the metal,
nothing happens, but a high-energy (high ν) photon
strikes with enough force to knock an electron loose.
22
Chapter 7 Notes

Examples: Energy of a Photon

3. What is the energy of a photon of radar radiation
with ν = 3.35×108 Hz?

Answer: 2.22×10-25 J
23

Examples: Energy of a Photon

4. (a) What is the energy (in kJ/mol) of blue light with
a wavelength of 432 nm? (b) If a single pulse of
this light delivers 5.00 mJ of energy, how many
photons does it contain? (sim. to Ex. 7.2)

Answer: (a) 277 kJ/mol; (b) 1.09×1016 photons

24
Chapter 7 Notes

Examples: Energy of a Photon

5. The biological effects of EM radiation become more
serious as the energy of the radiation increases:
Infrared radiation has a pleasant warming effect;
ultraviolet radiation causes skin to tan or sunburn;
and X rays and gamma rays (“ionizing radiation”)
can knock electrons from molecules, which can
seriously damage large biological molecules.
What energies (in kJ/mol) are associated with the
following wavelengths: infrared radiation (IR) with
λ=1.55 μm; ultraviolet (UV) light with λ=250 nm, X
rays with λ=5.49 nm, and gamma rays with
λ=0.0255 pm?
Answer: IR 77.2 kJ/mol; UV 479 kJ/mol; X-ray
2180 kJ/mol; γ-ray 4.69×109 kJ/mol
25

So, Is Light A Wave Or A Particle?

Yes. (????)
• In classical electromagnetic theory, light was
pictured as purely a wave phenomenon, with an
energy that was continuously variable.
– The wave model explains phenomena such as
refraction, diffraction, etc., that don’t make sense
by treating light as a particle.
• Now, we are suddenly picturing light as a shower of
particles, each having an energy of hν.
– The particle model explains blackbody radiation
and the photoelectric effect, that don’t make sense
by treating light as a wave.
• It is now known that in addition to behaving as
waves, light can also behave as small particles.
26
Chapter 7 Notes

Atomic Line Spectra

and the Bohr Model
of the Atom
27

Atomic Line Spectra

• At the same time that physicists were struggling to
understand light, chemists were trying to understand
the structure of matter from the atomic standpoint.
• One of the earliest clues to the arrangement of
electrons inside the atom came from the discovery of
line spectra.
• When an electric current is passed through a sample
of an element in the gas phase, the sample emits
light (e.g., neon or fluorescent lights). If this light is
passed through a prism, we see a line spectrum
(atomic emission spectrum), consisting of a series
of discrete lines separated by blank areas. (movie)

continuous spectrum line spectrum 28

Chapter 7 Notes

Atomic Line Spectra

Hg He H

29
Figure 7.9, 7.10

Atomic Fingerprints
• Each element has its own set of wavelengths of
radiation that it emits when energetically excited;
these spectral lines can be used as a “fingerprint” for
identifying that element.

Oxygen

Neon

30
Figure 7.12 Hydrogen
Chapter 7 Notes

31

Flame Tests and Fireworks

• The colors of a flame can be used to identify what
metal ions are present in a solution (flame test).
Na K Li Ba

Figure 7.13

• Metal salts are used in fireworks to produce different

colors.
• The element helium was first identified in the Sun,
before it was ever isolated on Earth, from its pattern
of lines in the solar spectrum.
32
MOV: Flame Tests for Metals
Chapter 7 Notes

Emission and Absorption Spectra

• Elements absorb the same wavelengths of light that
they radiate when they are heated. By passing white
light through a sample and observing what
wavelengths of light are subtracted from it, it is
possible to identify the elements in the sample.

emission
spectrum

absorption
spectrum

Mercury
33
Figure 7.14

The Balmer-Rydberg Equation

• The Balmer-Rydberg equation is an empirically
derived equation that allows us to predict the
position and wavelength of any of the lines in a
given series for the hydrogen atom:
1 ⎛ 1 1 ⎞
= R H ⎜⎜ 2 − 2 ⎟⎟
λ ⎝ n1 n2 ⎠
n1 and n2 are integers
RH = Rydberg constant = 1.097×10-2 nm-1

• Unfortunately, there was nothing to explain why this

equation worked, or why the hydrogen atom
produced line spectra as opposed to a continuous
spectrum.
34
Chapter 7 Notes

Examples: The Balmer-Rydberg Equation

6. What are the two longest-wavelength lines (in nm)
in the Lyman series (n1=1) of the hydrogen
spectrum?

1
λ
( ) ⎛1 1⎞
= 1.097 × 10 − 2 nm −1 ⎜ 2 − 2 ⎟ = 8.228 ×10 −3 nm −1
⎝1 2 ⎠
λ = 121.5 nm

1
λ
( ) ⎛1 1⎞
= 1.097 × 10 − 2 nm −1 ⎜ 2 − 2 ⎟ = 9.751×10 −3 nm −1
⎝1 3 ⎠
λ = 102.5 nm

35

Problem 3: Atomic Line Spectra

• Why does an atom emit only discrete wavelengths of
light, instead of a continuous spectrum?
Solution: The Structure of Atoms
• Since light is emitted by matter, the existence of line
spectra is related to the internal structure of the
atom. The behavior of light and the behavior of
electrons in atoms are therefore closely linked.
– To understand where line spectra come from, we
need a model for how electrons are arranged in
atoms, and the energy that the electrons possess.
– This led to the development of the Bohr model of
the atom, and then to quantum mechanics.

36
Chapter 7 Notes

The Rutherford Model of the Atom

Going Around in Circles
• Ernest Rutherford, after discovering the nucleus
(1911, Nobel Prize in Chemistry, 1908), proposed
that the atom looked like a miniature solar system,
with electrons orbiting the nucleus just like planets
orbiting the Sun. This was known as the
Rutherford Model of the atom.
e- • However, moving charges emit
EM radiation, and would
e-
continuously lose energy; in this
p+ e- model an electron would crash
n into the nucleus in about 10-10 s.
nucleus Since atoms are obviously more
stable than this, this model is
still not right.
37

The Bohr Model of the Hydrogen Atom

• In 1913, Neils Bohr (Nobel Prize, 1922) suggested a
model for the H atom that explained line spectra. In
this model, the energy levels in atoms are quantized,
having only certain allowed energy levels associated
with fixed electron orbits called stationary states.
– When an atom absorbs an amount of energy equal
to the energy difference between two fixed orbits
(E1), an electron jumps from the low energy orbit
(the ground state) to a higher-energy orbit (an
excited state).

energy is
E1 absorbed
nucleus nucleus

hν
38
ground state excited state
Chapter 7 Notes

The Bohr Model of the Hydrogen Atom

– When an atom releases energy, the electron falls
back down to the ground state, releasing a photon
of light which corresponds exactly to the energy
difference (E1) between orbits.

energy is
E1 released
nucleus nucleus

hν

excited state ground state

• In this model, line spectra arise because the atom’s

energy has only certain discrete levels, and atoms
can absorb or emit energy only in these “chunks.”
39

The Bohr Model of the Hydrogen Atom

What a Bohr

40
Figure 7.11
Chapter 7 Notes

The Bohr Model of the Hydrogen Atom

• The Bohr model rationalized the existence of line
spectra, and mathematically predicted the
wavelengths of radiation emitted by the hydrogen
atom in its line spectrum:
2 π 2 me e 4 2π 2 me e 4 ⎛ 1 1 ⎞
E=− ΔE = ⎜ − ⎟
n2h2 h 2 ⎜⎝ n12 n2 2 ⎟⎠
• Unfortunately, the Bohr model couldn’t explain
where these fixed electron orbits came from, and
failed to predict the location of line spectra for
elements with more than one electron.
• Ultimately, the ideas behind the Bohr model became
incorporated into quantum mechanics.

41

Quantum Quotes
Anyone who is not shocked by quantum
mechanics has not understood it.
Niels Bohr

The theory of quantum electrodynamics

describes nature as absurd from the point of
view of common sense. And it agrees fully with
experiment. So I hope you can accept nature as
she is — absurd.
Richard Feynman

42
Chapter 7 Notes

The Wave Nature

of Matter:
Quantum Mechanics
43

The Wavelike Properties of Matter

• So now we have light having properties of waves
and of particles. Louis de Broglie (1924, Nobel
Prize, 1929) further blurred the distinction between
matter and radiant energy by suggesting that if light
can have particle-like properties, then matter can
have wave-like properties.
• By combining the Planck equation for the energy of
a photon, Einstein’s equation for the relationship of
mass and energy, and the relationship between ν and
λ, and replacing the speed of light (c) with the speed
of a particle (v), we obtain:
E = hν E = mc2 c = λν
h
λ= the de Broglie relation
mv
44
Chapter 7 Notes

Examples: de Broglie Wavelength

7. Calculate the de Broglie wavelength in nm of:
a. an electron with a speed of 2.2×106 m/s.
(me = 9.11×10-31 kg) and
b. a two ton car (909 kg) moving at 55.0 mi/hr
(24.5 m/s). (sim. to Ex. 7.4)

Answer: (a) 0.331 nm; (b) 2.96×10-29 nm

45

Electron “Waves”
• Electrons are particles, and have a mass associated
with them. However, they can diffract just like light
does, and produce interference patterns, which
means they have wave properties. [movie]
– In 1927, Clinton Davisson and George Thomson
demonstrated electron diffraction by scattering
electrons off a nickel crystal (Nobel Prize, 1937).
[Thomson was the son of J. J. Thomson, who won a Nobel Prize for
the discovery of the electron.]

46
Figure 7.15
Chapter 7 Notes

Wave-Particle Duality
• Thus, both light and matter exhibit wave-particle
duality: they are both wave-like and particle-like.
• For matter with large masses (like baseballs or
people) the de Broglie wavelength is so small that
wave-like properties are negligible, and they behave
“entirely” like particles.
• For matter with small masses (like electrons or
protons) the de Broglie wavelength is large enough
to be measurable, and the wave properties of these
particles become important.
• In order to model how electrons are arranged inside
atoms, we have to take into account both their
particle properties and their wave properties.

47

The Quantum Mechanical Model of the Atom

• The wave and particle descriptions of matter and
energy were combined independently by Erwin
Schrödinger in 1926 (Nobel Prize, 1933) and
Werner Heisenberg in 1927 (Nobel Prize, 1932) in
the quantum mechanical model of the atom.
– Quantum mechanics is the branch of physics
which describes the properties of light and matter
at the atomic scale.
– Quantum mechanics unifies the particle and wave
models into a single description of reality.
• In quantum mechanics, we abandon the notion of an
electron as a small particle moving around the
nucleus in a defined path and concentrate on its
wave-like properties.
48
Chapter 7 Notes

The Heisenberg Uncertainty Principle

Heisenberg May Have Slept Here
• Heisenberg showed that it is impossible to know
simultaneously the exact position and velocity of a
particle. This is known as the Heisenberg
Uncertainty Principle.

(Δx )(m Δv ) ≥ h
4π
Δx = uncertainty in position along the x-axis
m = mass of object
Δv = uncertainty in velocity

• Position and velocity are said to be complementary

properties: the more you know about one, the less
you know about the other.

49

The Meaning of the Uncertainty Principle

• What the uncertainty principle implies is that we can
never know both the position and the velocity of an
electron beyond a certain level of precision.
– If we know the velocity with a high degree of
certainty, the position must be uncertain.
– If we know the position exactly, we can’t know
the velocity.
– As a result, the electron always appears as
something of a blur when we attempt to make a
physical measurement of its position and velocity.
• Essentially, we observe either the particle or the
wave behavior, but not both at the same time.

50
Chapter 7 Notes

The Meaning of the Uncertainty Principle

• In classical physics, particles move in well-defined
trajectories determined by the particle’s velocity and
position. In quantum mechanics, however,
trajectories are replaced by probability distribution
maps, where the density of the dots indicates the
probability of finding the particle.

Figure 7.17

• We cannot assign fixed paths (such as orbits) for

electrons in atoms; all we can do is determine
probabilities for finding electrons at various points
in a region of space around the atom. [movie]
51

The Schrödinger Wave Equation

• The quantum mechanical model is framed in the
form of the Schrödinger wave equation.
⎛ h 2 ⎞⎛ ∂ 2 ψ ∂ 2 ψ ∂ 2 ψ ⎞
Hψ = Eψ − ⎜⎜ ⎟⎟⎜⎜ 2 + 2 + 2 ⎟⎟ + Vψ = Eψ
⎝ 2 m ⎠ ⎝ ∂x ∂y ∂z ⎠
• The solutions to the wave equation are called wave
functions, or orbitals, represented by the Greek
letter ψ (psi). These are equations that encode
what’s known about a particle with a given energy.
• The Schrödinger equation can be solved exactly only
for the hydrogen atom (one proton and one electron),
but very good approximate solutions for multi-
electron atoms can be found starting with the basic
functions for the hydrogen atom.
52
Chapter 7 Notes

The Schrödinger Wave Equation

• The probability of finding an electron within a
certain region of space in an atom is given by ψ2.
Probability of finding
Wave Solve Wave function
electron in a region
equation or orbital (ψ)
of space (ψ2)
+∞

∫ ψ dx dy dz = 1
2

−∞

53

Quantum Quotes
If someone says that he can think about
quantum physics without becoming dizzy, that
shows only that he has not understood anything
whatever about it.
Niels Bohr

This inability to imagine quantum goings-on led

to the popular perception that the realm of
the inner atom is fuzzy, elusive, murky, and
uncertain. On the contrary, most physicists
would agree that what quantum theory has
brought to science is exactly the opposite —
concreteness and clarity.
K. C. Cole, First You Build a Cloud and Other
Reflections on Physics as a Way of Life (1999) 54
Chapter 7 Notes

Quantum Numbers

55

Quantum Numbers and Atomic Orbitals

• A wave function for an electron in an atom is called
an atomic orbital; this atomic orbital describes a
region of space in which there is a high probability
of finding the electron.
• Each electron in an atom is described by four
different quantum numbers.
– Principal quantum number, n: energy and size.
– Angular momentum quantum number, l: shape.
– Magnetic quantum number, ml: orientation in space.
– Spin quantum number, ms: orientation of spin axis.
• The first three (n, l, ml) specify the particular orbital
of interest, and the fourth (ms) specifies how many
electrons can occupy that orbital.
56
Chapter 7 Notes

Principal Quantum Number, n

• The Principal Quantum Number, n is an integer
that can range from 1 to infinity:
n = 1, 2, 3, …, ∞.
• It specifies the size and energy level of an orbital.
– For one-electron atoms, such as H, the energy
depends only on n; for atoms with more than one
electron, the energy depends on both n and l.
– As n increases, the number of allowed orbitals
increases and the size of those orbitals increases,
allowing an electron to be farther from the
nucleus; this requires it to be higher in energy.
• All orbitals that have the same value of n are said to
be in the same shell (level).
• The total number of orbitals for a given n value is n2.
57

Principal Quantum Number, n

• For the hydrogen atom, the energy of an electron in
an orbital with a value n is

( )⎛ 1 ⎞
En = − 2.18 × 10 −18 J ⎜ 2 ⎟
⎝n ⎠
(This energy is negative because the energy of the
hydrogen atom is less than the energy of the separate
proton and electron.)

58
Chapter 7 Notes

Angular Momentum Quantum Number, l

• The Angular-Momentum Quantum Number
(a.k.a. secondary or azimunthal), l, is an integer that
ranges from 0 to n-1:
l = 0, ..., n-1.
• It specifies the shape of an orbital with a particular
value of n.
• The angular-momentum quantum number divides
the shells into smaller groups of orbitals called
subshells (sublevels).
• Usually, a letter code is used to identify l to avoid
confusion with n:
l 0 1 2 3 4 5 ...
Letter s p d f g h ...
59

Angular Momentum Quantum Number, l

• Examples:
– If n=1, the possible values for l are 0.
– If n=2, the possible values for l are 0 and 1.
– The subshell with n=2 and l=1 is the 2p subshell
– If n=3 and l=0, it is the 3s subshell, and so on.
• The value of l also has a slight effect on the energy
of the subshell; the energy of the subshell increases
with l (s < p < d < f).

60
Chapter 7 Notes

Magnetic Quantum Number, ml

• The Magnetic Quantum Number, ml, is an integer
which runs from -l to +l:
ml = -l, ..., 0, ..., +l.
• It specifies the orientation in space of an orbital of
a given energy (n) and shape (l).
• This number divides the subshell into individual
orbitals which hold the electrons. There are 2l+1
orbitals in each subshell, and n2 orbitals in each
shell.
• Thus the s subshell has only one orbital, the p
subshell has three orbitals, and so on.

61

The First Three Quantum Numbers

• This diagram summarizes the available orbitals in
the shells from n=1 to n=3:

62
Chapter 7 Notes

Spin Quantum Number, ms

• The Spin Quantum Number, ms, has only two
possible values:
ms = +½ (↑, spin up) or -½ (↓, spin down)
• It specifies the orientation of the spin axis of an
electron.
– Because an electron spins either clockwise or
counter-clockwise, it creates a tiny magnetic
field, which can be oriented either up or down.
– ms tells us how many electrons can occupy a
particular orbital.

63

Spin Quantum Number, ms

• The Pauli exclusion principle (Wolfgang Pauli,
1925, Nobel Prize 1945) states that no two electrons
in an atom can have the same values for all four of
the quantum numbers. This means that:
– Since two electrons in the same orbital have three
of the same quantum numbers (n, l, and ml), they
must have opposite spins (the spins are paired).
– An orbital can hold at most two electrons.
• Substances in which all electrons are paired are
diamagnetic — they are not attracted to magnets.
• Atoms with more electrons that spin in one direction
than another contain unpaired electrons. These
substances are paramagnetic — they are weakly
attracted to magnets. [movie]
64
Chapter 7 Notes

Table of Allowed Quantum Numbers

Number of Orbital Number of
n l ml orbitals Name electrons
1 0 0 1 1s 2
2 0 0 1 2s 2
1 -1, 0, +1 3 2p 6
3 ____ ____________ ____ ____ ____
____ ____________ ____ ____ ____
____ ____________ ____ ____ ____
4 ____ ____________ ____ ____ ____
____ ____________ ____ ____ ____
____ ____________ ____ ____ ____
____ ____________ ____ ____ ____
5 ____ ____________ ____ ____ ____
____ ____________ ____ ____ ____
____ ____________ ____ ____ ____
____ ____________ ____ ____ ____
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____ ____________ ____ ____ ____

Examples: Quantum Numbers

8. Each of the following sets of quantum numbers is
supposed to specify an orbital. However, each set
contains one quantum number that is not allowed.
Replace the quantum number that is not allowed
with one that is allowed. (For Practice 7.6)

a. n = 3, l = 3, ml = +2

b. n = 2, l = 1, ml = -2

c. n = 1, l = 1, ml = 0

d. Is there any such thing as a 3f orbital?

e. What are the allowed subshells when n = 7?

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Chapter 7 Notes

Quantum Mechanics and Line Spectra

• In the quantum mechanical model of the atom, each
wavelength in a line spectrum corresponds to an
energy transition between orbitals.
– When at atom in its ground state absorbs energy,
an electron in a lower energy level is promoted to
a higher-energy orbital in an excited state.
– The energetically excited atom is unstable, and
goes back to the ground state by emitting this
excess energy as a photon of EM radiation.

67
Figure 7.20

Quantum Mechanics and Line Spectra

– The energy difference between the excited state
and the ground state corresponds to the energy of
the photon (hν) which is emitted.
• The frequencies of light in line spectra correspond to
the energy differences between the orbitals in the
atom. [movie]

68
Figure 7.21
Chapter 7 Notes

The Shapes of
Orbitals

69

l = 0: the s orbital
• All s orbitals are spherical; since there is only one
“direction” for a sphere to point in, the only allowed
value for ml is 0, and there is only one s orbital per
shell (1s, 2s, 3s, 4s, etc.)
• The image below represents the probability density
of finding an electron in a region of space
surrounding the nucleus. The further away we move
from the nucleus, the lower the probability is of
finding an electron.

70
Figure 7.15
Chapter 7 Notes

l = 0: the s orbital
• Atomic orbitals are often represented
by geometric shapes that cover a region
of space inside of which there is a 90%
probability of finding an electron.

Figure 7.23

• The radial distribution function in

Figure 7.24 shows the total
probability of finding the electron
within a spherical shell at a distance
r from the nucleus.
– The maximum probability of finding
an electron in an H atom occurs at a
distance of 52.9 pm from the nucleus.
71
Figure 7.24

l = 0: the s orbital
• At higher values of n, the s orbitals have more
spherical regions of high probability of finding an
electron, separated by surfaces of zero probability
called nodes, where there is zero probability of
finding an electron.
– A node corresponds to a zero-amplitude part of a
standing wave or a vibrating string (like a guitar
string).

72
Chapter 7 Notes

l = 0: the s orbital
• A 2s orbital is larger
than a 1s orbital, and
has two high-
probability regions
for finding electrons,
separated by one
node.
• A 3s orbital is even
larger, and has three
high-probability
regions separated by
two nodes.

73
Figure 7.25

l = 1: the p orbitals
• When l = 1, ml = -1, 0, or +1. There are three p
orbitals at each energy level (except for n=1).
• The p orbitals are dumbbell-shaped, with their
electron distributions concentrated in identical lobes
on opposite sides of the nucleus, separated by a
nodal plane. The p orbitals are all perpendicular to
each other, aligned along the x, y, and z axes.

74
Figure 7.26
Chapter 7 Notes

l = 2: the d orbitals

75
Figure 7.27

l = 3: the f orbitals

76
Figure 7.28
Chapter 7 Notes

Why Atoms are Spherical

• If all of the orbitals are superimposed on each other,
a roughly spherical shape emerges:

77
Figure 7.29

The End

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