17.

The Wave Model of the Atom

Rutherford discovered the nucleus and Bohr con-
ceived an atom which resembled a tiny solar system, but
with the important difference that only certain orbits
were allowed. Within these orbits, the electrons seemed
to violate the known phenomenon that accelerated
charged particles should radiate away their energy very
quickly as electromagnetic radiation. De Broglie soon
introduced the idea of matter waves and demonstrated
that Bohr’s orbits for the hydrogen atom were only those Figure 17.1. Standing waves created when waves of the
for which the wavelength of the electron fit exactly. same wavelength move through a string from opposite
We now conclude our development of the model of ends. The solid and dashed curves show the string at
the atom. But first we describe a phenomenon called two different times.
“standing waves.” This represents the missing piece
that will complete our model of the atom as we current-
ly understand it. In later chapters we will begin to study
matter as the chemist works with it. We will discover
certain puzzling patterns in the behavior of the chemical
elements and see that these are explained by the model
of the atom that we are now developing.

Standing Waves

When waves of the same wavelength coming from

different directions move through a common medium, a
phenomenon we call interference occurs. Imagine a
string being shaken with the same frequency at both
ends so that waves meet in the middle as in Figure 17.1.
If done correctly, we get stationary points (called
nodes) of destructive interference as well as large-
amplitude oscillating points (called antinodes) of con-
structive interference. We can get the same effect by
shaking only one end and reflecting the wave back on
itself from a stationary end. When the wavelength is
just right, allowed patterns called “standing waves”
occur on a string with stationary ends (Fig. 17.2).
Patterns associated with “incorrect” wavelengths are
not allowed. From the way we have described their ori-
gin, one realizes that the standing waves are dynamic
phenomena, but the pattern of nodes and antinodes
remains stationary.
Standing waves can also occur in two-dimensional
media such as a drumhead that is fixed around the
periphery. In such instances the nodes are lines rather
than points, but the idea is the same (Fig. 17.3).
Although it is harder to imagine, such standing waves
Figure 17.2. To get standing waves between two sta-
tionary points at the ends of a string, the wavelengths
must just fit the space between the points. The upper
and middle waves are allowed; the lower wave is not
allowed.
can also be set up in three-dimensional media. In fact,
about a hundred years ago Hermann von Helmholtz
(1821-1894) made detailed studies of the vibrations of
air enclosed in rigid metal spheres.
The probability waves described by Schrödinger’s
equation can set up standing waves, too. A place where
the proper conditions occur is in the atom. In the atom
these standing waves of probability are called orbitals.
The al ending shows that an orbital is not an orbit (i.e.,

155

Figure 17.3. Standing waves in a two-dimensional
medium.
not a path of movement), but rather a description of the
probability of the position of the electron.
The orbitals are the final pieces in our puzzle of the
atom. Whenever we “look” at an electron (including
looking with instruments), the electron reveals itself as
a particle. When we don’t look, the only knowledge we
have about the electron is what is contained in its
probability wave (or, to be more precise, “wave func-
tion”). Thus, when the electron exists in the unobserved
atom, we cannot think of it as a charged particle moving
in a well-defined orbit. All that exists is the orbital, i.e.,
a standing wave of probability satisfying the
Schrödinger equation. We are then freed from the prob-
lem that plagued the nuclear atom from its inception:
Why doesn’t the electron radiate its energy as we expect
a charged particle to do when it accelerates in an orbit?
The answer: There are no orbits; hence, there is no
problem. The idea of an orbit has no reality in an unob-
served atom.
Standing waves in a string are the result of vibra-
tions of the pieces of the string relative to their equilib-
rium points. The standing waves of the Schrödinger
equation do not result from vibrations in the positions of
the electron or of any medium. The waves simply
denote the probability that the electron described by the
orbital could be found at a particular point in space.
One way of thinking of an orbital is to think of a
cloud surrounding the nucleus. In basic terms think of
a spherical cloud in the volume of space around a nucle-
us where an atomic electron could be expected. This
electron cloud is a mental constraint, not a physical real-
ity. The cloud is dense in some places and not so dense
in others, particularly as we recede from the nucleus.
The density of the cloud near a point in space around the
nucleus can be thought of as being proportional to the
probability of finding the electron there. At large dis-
tances from the nucleus, the probability gets very low,
so the cloud gets very thin, but it never quite fades into
nothing. The solution of the Schrödinger equation
yields the numbers that represent the density of this
cloud for all points in space. For most atoms other than
156
the simplest, computers are required to solve the equa-
tion which yields the probability densities.
Orbitals
There are a few technical details to discuss at this
point. There are various kinds of standing wave pat-
terns that are allowed within the atom. A few are shown
in Figure 17.4. For historical reasons they are labeled
“s,” “p,” “d,” “f,” and so forth. In fact there are three
variations of the p orbitals and five variations of the d
orbitals. In these drawings the nucleus is a tiny point
near the center of the pattern. The shaded regions of the
orbital patterns are regions of probability where the
electron is likely to be found if we were to look. We do
not think of the electron moving in these patterns; they
simply describe probabilities. The drawings of the
orbitals do not display the fact that they do not have
sharp boundaries. The diagrams in Figure 17.4 show
the three types of orbitals by indicating the “skin” that
encloses the volume inside which the electron will be
found 90 percent of the time. Within the spherical s-
orbital, the electron is far more likely to be found near
the center than near the skin. Electron probability is not
evenly distributed in the other two orbitals either.
Discussing the size of an atom becomes difficult
because there is really no outer boundary beyond which
the electron can never be found.
Figure 17.4. Shapes of three orbitals: s-orbital (spher-
ical), p-orbital (three-dimensional dumbbell), d-orbital
(rounded cloverleaf).
There is also a technicality, called the Exclusion
Principle, that does not allow more than two electrons
to exist in orbitals which occupy exactly the same space
at the same time. In those cases where two electrons
existing as orbitals try to occupy the same space at the
same time, the electrons must differ in a characteristic
called “spin,” a characteristic that is similar to the spin-
ning of a ball on its axis. The spinning of electrons can
be referred to in two ways, either as “spin up” or “spin
down.” These are analogous to a ball spinning either is identified with a unique label. Once the electron has
clockwise or counterclockwise about an axis. fallen into the atom and lost energy by emitting pho-
When an electron exists in one of these orbitals, it tons, it is stuck like the ball in the sink, until energy is
possesses a unique amount of energy, called the orbital added.
energy. Different orbitals correspond to different elec- The energies associated with the levels are predict-
tron energies. In this way the model retains the essen- ed by the Schrödinger equation. Some of these levels
tial feature of the Bohr atom which explained the dis- cluster together and are said to belong to the same
crete spectrum of hydrogen. The discrete colors are “shell.” Within each shell the electron can exist in an
formed as an electron that has been bumped to a higher orbital. The pattern is that in Shell 1 there is one s-
energy orbital makes a jump from a higher energy orbital; in Shell 2 there are one s-orbital and three p-
orbital to an unoccupied lower energy orbital. In order orbitals; in Shell 3 there are one s-orbital, three p-
to rid itself of the energy difference, the atom creates orbitals, and five d-orbitals; and so on. Generally, the
and emits a photon of frequency (and, hence, color) that orbitals get larger as the shell number increases.
just corresponds to the energy difference according to Although s-orbitals belonging to Shell 1 and to Shell 2
the equation which proved to be so important in are both spherical, they are not of the same size and do
explaining the photoelectric effect: not occupy exactly the same space. Thus, the Exclusion
Principle does not apply to orbitals that belong to dif-
ferent shells.
E2 ! E1 " Planck’s constant # frequency .
Figure 17.5 shows an energy level diagram for
hydrogen with some of the possible energy levels. Only
Energy Wells
one energy state is actually occupied by an electron.
Electrons in these diagrams are represented with either
Now, imagine a lecture demonstration table
a “spin up” symbol (arrow pointing up) or a “spin
that contains a sink. Visualize a ball on the table poised
down” symbol (arrow pointing down). The occupied
at the edge of the sink. Gently nudge the ball so that it
energy state in Figure 17.5 is in Shell 1, s-orbital, and is
falls into the sink and comes to rest at the bottom. Does
designated “1s.”
the ball now have more or less energy than it had before
falling into the sink? The essential change has been in
the gravitational potential energy, which is less at the
bottom of the sink than at the elevated position on the
table top. Therefore, the ball has less energy inside the
sink. Once this energy difference has been lost, the ball
is stuck in the sink and will remain there until someone
or something comes along to replace the missing gravi-
tational potential energy by lifting it out of the sink.
Now imagine another sink located below the
first, so that occasionally the ball will fall through the
drain of the first to land below in the second. Now the
ball has less energy than it had in the first sink. Imagine
a series of sinks which are gradually lower. In this ar-
rangement we could label each sink with the energy the
ball has at that particular level, a sequence that is
decreasing as the ball falls to lower and lower levels.

Orbital Energies
Figure 17.5. A schematic energy level or energy well
diagram for a one-electron atom. Each horizontal line
In many ways an electron in an atom is like the ball
(level) represents a possible energy of an electron in the
dropping into a sink or a well. The electron has more
atom. Different electron energies correspond to differ-
energy when it is free than when it has become a part of
ent electron orbitals.
the atom. The force pulling the electron into the atom
is electrical rather than gravitational as it is in the sink
The same labeling scheme can be applied to atoms
analogy. And in the atom there are no sinks, just orbi-
of other elements (helium, lithium, and so forth), but the
tals. But depending on the particular orbital, the elec-
energies associated with each level differ from element
tron has a certain, specific energy called an “energy
to element. In Figure 17.6 the energy level diagrams for
level.” Thus, we often represent an atom by an energy-
hydrogen (one electron), helium (two electrons), lithi-
level or energy well diagram (see Fig. 17.5). Each level
um (three electrons), and beryllium (four electrons) ar

157
Figure 17.6. Energy level diagrams for hydrogen, heli-
um, lithium, and beryllium.

side by side for comparison. Figure 17.7 is an extension

of Figure 17.6.
The p-orbitals always come as triplets; the basic
three-dimensional dumbbell comes in three spatial ori-
entations. Each orientation of orbital can contain two
electrons if one is spin up and one is spin down. The
orientations of p-orbitals in a given shell have the same
energy. So we can have up to six electrons in an atom
in a triplet of p-orbitals with essentially the same ener-
gy. The d-orbitals come in a quintuplet of shape-orien-
tation combinations. We can have up to ten electrons in
an atom in a quintuplet of d-orbitals with basically the
same energy.
Let us summarize what has been said about the
orbitals of a single atom such as magnesium (see Fig.
17.8). The s-orbitals are spherical; 1s is always the low-
est energy orbital, and 2s is the next lowest energy
orbital. The p-orbitals are shaped like dumbbells and
the lowest energy of these is the 2p; it has energy just
greater than that of the 2s orbital. The 3s orbital has the
next highest energy after the 2p orbital, and so on.
Figure 17.8. Energies of the s and p orbitals for a mag-
nesium atom.
An electrically neutral magnesium atom will have
just as many electrons as protons (both given by the
atomic number). The electrons will be found in the low-
est-energy orbitals available and will pair up in sets of
two (spin up, spin down) if necessary. Many vacant
orbitals of higher energy will remain. Absorbed light or
collisions with other atoms or particles can cause low-
lying electrons to be excited to the higher energy vacant
orbitals, or even to leave the atom entirely (ionization).
In each unit of time there is some probability that the
electron will spontaneously return to any vacancy avail-
able at lower levels. When the quantum mechanical

Figure 17.7. Energies of occupied orbitals of light elements.

158
dice-thrower of Chapter 16 rolls the magic combination,
one of the possibilities becomes reality and the electron
jumps. In doing so it emits light, and this accounts for
observed emission line spectra.
Chemical Elements
Historically, the development of a model of atoms
came quite late. Long before the physicists had worked
out the details of atomic structure, chemists were work-
ing with things they too called “atoms.” However, the
definition of “atoms” was not clear. For example, if
there were things called “atoms” it was quite possible
that all substances (gold, hydrogen, carbon, and others)
were made of identical atoms that somehow combined
in different ways to create the different chemical char-
acteristics of the substances. If there were different
atoms for different substances, then it was quite feasible
that the atoms of a given substance were nevertheless
different in size. If each substance had atoms of con-
sistent size, there was still no way to tell whether that
size was large or small. It was possible that the atoms
were fluffy things like tufts of wool, which were in
physical contact. It was also possible that they were
much smaller things that moved about in chaotic motion
and only came in contact by collision. These theories
had to be resolved by clever people throughout the cen-
turies.
Robert Boyle is credited with giving us the modern
idea of an element in the year 1661. He said an element
is any substance that cannot be separated into different
components by any known methods. John Dalton made
the connection much later (ca. 1803) between elements
and atoms. He took the atoms of a particular substance
to be identical and defined an element to be a substance
composed of only one kind of atom.
Today, the atoms are modeled with Schrödinger’s
equation. Each time an additional positive charge (pro-
ton) is added to the nucleus, the equation predicts
orbitals with new energy levels that are unique to the
number of protons used in the nucleus. Thus, today we
define an element to be: a group of atoms all having the
same number of protons.
It is also important to note what has been left out of
this definition. Electrons were left out because one (or
a few) can be removed easily and just as easily replaced
from moment to moment. Mass was left out because it
depends on the number of nucleons in the nucleus
(including neutrons), and the number of neutrons may
vary from nucleus to nucleus of an element despite the
fact that the number of protons does not.
You are no doubt familiar with some of the more
than 100 known chemical elements. Most of the com-
mon metals are elements: copper, tin, aluminum, and
nickel. Steel is nearly pure elemental iron, but it contains
small amounts of other metals and carbon. Alloys are
159
mixtures of a least two metallic elements: brass (copper
and zinc); solder (lead and tin); and the gold in jewelry,
which has had silver or copper added to harden it.
Some common nonmetallic elements are carbon in
the form of charcoal, graphite, or diamond; nitrogen and
oxygen (gases comprising over 90 percent of the air we
breathe); and sulfur, a yellow substance.
The names of the elements are listed in Appendix
B. Notice that each element has its own symbol, which
is usually an abbreviation of its name. For example,
hydrogen is H, helium is He, and so forth. Some ele-
ments have symbols that are based on their Latin names:
sodium (natrium) is Na and potassium (kalium) is K.
People working with the symbols of the chemical
elements sometimes add to an element’s symbol with
numerical subscripts and superscripts indicating how
many of the atomic building blocks are present in a par-
ticular atom. The atomic number is the number of pro-
tons in the atom and is usually written low and in front
of the symbol: 1H, 2He, 6C. The mass number is the
number of nucleons (neutrons + protons) in the nucleus.
It is approximately equal to the atomic mass expressed
in atomic mass units (amu) (see Appendix B). The mass
number is usually (but not always) written higher up
and in front of the symbol: 1H, 4He, 3He. Notice that
two atoms of the same element (helium in this case)
may have different mass numbers because, within lim-
its, they may have different numbers of neutrons.
A superscript following the symbol is often used to
designate the excess or deficiency of electrons com-
pared to the neutral atom. A neutral helium atom could
be written He0, but the 0 is usually left off neutral atoms.
If the atom has an extra electron it will have a negative
charge, and the resulting ion will be designated He1–.
On the other hand, if helium loses an electron, it will
have a positive charge and be represented by He1+.
Helium could lose both its electrons and be He2+. It
would then be an alpha particle, the particle Rutherford
used to probe the atom and discover the nucleus. When
it is required, the symbol can be given numbers in all
three positions: 42He2+.
Summary
Orbitals are standing waves of electron probability
established in the atom in a way specified by
Schrödinger’s equation. Each orbital corresponds to a
specific energy that the electron has when it occupies
the orbital. The orbital patterns are discrete and so are
the energies associated with them.
Electrons in an atom can be thought of as being in
a kind of energy well. They have less energy while in
an atom than they have when they are free of the atom.
To free an electron from an atom (ionization), we must
supply enough energy to remove it from its well.
A chemical element is a group of atoms all having
the same number of protons. Schrödinger’s equation
predicts different energy levels for atoms with different
numbers of protons in the nucleus. This happens
because differing amounts of charge on the nucleus
exert differing strengths of electromagnetic interaction
with the electrons of the atom. Thus, for each chemical
element there is a unique atom with its own characteris-
tic energy levels.
STUDY GUIDE
Chapter 17: The Wave Model of the Atom
A. FUNDAMENTAL PRINCIPLES
1. The Wave-Particle Duality of Matter and
Electromagnetic Radiation: See Chapters 14 and
16.
2. The Exclusion Principle: No more than two elec-
trons may occupy orbitals that occupy the same
space at the same time. Two electrons which do
occupy the same orbital must differ in their spin.
B. MODELS, IDEAS, QUESTIONS, OR APPLICA-
TIONS
1. The Wave Model of the Atom: That model of the
atom in which the electrons are described by
orbitals, i.e., standing probability waves. In the
Wave Model of the Atom, the electrons in the atom
have discrete energies and obey the Exclusion
Principle.
2. What are standing waves?
3. What are standing waves of probability?
4. Why are only certain “orbitals” allowed?
5. What is an “unwatched” electron doing?
6. How many electrons can be associated with a sin-
gle orbital?
7. How is an electron in an atom classified or given an
“address?”
8. What is an energy well?
C. GLOSSARY
1. Antinode: The positions of constructive interfer-
ence in a standing wave. On a violin string, the
antinodes are the positions of maximum vibration
of the string.
2. Atomic Number: The number of protons in an
atom.
3. Chemical Element: A substance consisting of
atoms, all of which have the same number of pro-
tons.
4. Energy Well: A conceptual model for visualizing
the discrete energies of electrons in an atom.
Electrons within an atom have less energy than
they have when free of the atom, much like a ball
which has fallen into a well.
5. Mass Number: The combined number of protons
and neutrons in the nucleus of an atom.
160
6. Node: The positions of destructive interference in
a standing wave. For waves in a one-dimensional
medium, such as a violin string, the nodes are
points on the string that are not vibrating.
7. Orbit: See Chapter 15.
8. Orbital: A standing wave pattern of the probabili-
ty waves which describe electrons in an atom.
9. Orbital Energy: The discrete energy that an elec-
tron has when it is described by a particular orbital.
10. Probability Wave: See Chapter 16.
11. Shell: A grouping of energy levels within an atom.
Electrons having orbital energies within this group-
ing are said to belong to the same shell.
12. Spin: A characteristic of electrons which has some
similarity to the spinning of a ball on an axis
through its center. For an electron, however, there
are only two possible ways of “spinning.” One is
called “spin-up” and the other “spin-down.”
13. Standing Wave: A pattern of constructive and
destructive interference of waves for which the
positions of constructive and destructive interfer-
ence do not move.
D. FOCUS QUESTIONS
1. What is a standing wave? What is an orbital? (What
is the connection between a standing wave and an
orbital?) Why are only certain orbitals available in
an atom? Describe the energy changes that occur
when an electron associated with one orbital goes
to a different orbital.
2. Carefully outline the main elements of the Wave
Model of the Atom. Draw a simple energy well
representing an atom. What do the horizontal lines
in the energy well figure represent? Describe what
happens to the energy of an electron when it moves
and is then associated with an orbital higher in the
energy well.
E. EXERCISES
17.1. Does Figure 17.4 depict surfaces on which the
electron in an atom travels? If not, what do the surfaces
represent?
17.2. What scientific principle suggests that it is
impossible to know simultaneously both the position
and velocity of an electron in an atom?
17.3. Which of the letters—s, p, d, or f—designates
an orbital shaped like a rounded, four-lobed cloverleaf?
17.4. Why can’t an electron remain at a fixed posi-
tion outside the nucleus?
17.5. Why can’t an electron revolve indefinitely
around the nucleus in orbit?
 17.6. If an electron is in a spherically shaped orbital
(e.g., Fig. 17.4), is it possible for the electron sometimes
to be outside the spherical skin?
17.7. Is there any possibility that an electron from
an atom in this paper could be on Mars for a moment
today?
17.8. Draw a diagram like Figure 17.5 showing
only 1s, 2s, 2p, and 3s orbitals (all unfilled). Put in
enough electrons to represent Li. Note the single elec-
tron in the 2s orbital. A similar element should have the
orbitals filled until there is one electron in the 3s orbital.
How many more electrons are required to fill orbitals
until there is one electron in 3s? What neutral element
has this many electrons?
17.9. A neon sign is simply a glass tube filled with
neon gas. When electricity is passed through, it
becomes a discharge tube. The electrons in the neon
atoms are raised to higher levels. Explain why the tube
then glows red and why, if the tube is filled with xenon
gas, different colors are emitted.
17.10. Which atoms in Figure 17.7 have filled
shells? Which have unfilled shells? Would more ener-
gy be required to remove the highest energy electron in
a filled shell or an unfilled shell?
17.13. Which element has the same number of elec-
trons in an s-orbital as beryllium, Be?
17.14. Which element has the same number of elec-
trons in a p-orbital as boron, B?
17.15. The atomic number of nitrogen is 7. How
many electrons does one of its atoms have? How many
protons? How many neutrons? State the pattern or rela-
tionship among these numbers and check to see if all of
the other atoms in Table 17.1 follow this pattern.
17.16. If you know how many protons an atom has,
what else must you know to calculate its mass number?
17.17. Use Table 17.1 or Appendix B when neces-
sary to complete Table 17.2.
17.18. Use Appendix B to decide which of the fol-
lowing are elements:
(a) lead
(b) arsenic
(c) bronze
(d) radon
(e) potash
(f) platinum
(g) mercury
(h) freon

17.11. Which atom in Figure 17.7 has the lowest 17.19. Which of the following is the most complete
energy vacancy (the deepest unfilled well)? model of the atom?
(a) solar system
17.12. Which two atoms in Figure 17.7 have no (b) nuclear model
vacant orbitals of low energy and no electrons in high (c) Bohr model
energy orbitals? Would you expect these atoms to par- (d) wave model
ticipate readily in chemical reactions? (e) all of the above are equally complete.

Table 17.1. Components and masses of atoms. To be used in Exercise 17.15.

ATOMIC NUMBER OF NUMBER OF NUMBER OF MASS

NUMBER NAME ELCTRONS PROTONS NEUTRONS NUMBER

1 Hydrogen 1 1 0 1
2 Helium 2 2 2 4
3 Lithium 3 3 4 7
4 Beryllium 4 4 5 9
5 Boron 5 5 6 11
6 Carbon 6 6 6 12
7 Nitrogen 7 7 7 14
8 Oxygen 8 8 8 16
9 Fluorine 9 9 10 19
10 Neon 10 10 10 20
11 Sodium 11 11 12 23

161
Table 17.2. To be completed with Exercise 17.17.

ATOMIC NUMBER OF NUMBER OF MASS NUMBER OF

SYMBOL NAME PROTONS NEUTRONS NUMBER ELCTRONS

6C 6 6

Oxygen 8 8
20
10Ne 10

He2+ Helium ion 2

Nitrogen 7 8

9F1– 9 10
27
13Al3+

162