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

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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
Figure 17.3. Standing waves in a two-dimensional near the center of the pattern. The shaded regions of the
medium. orbital patterns are regions of probability where the
electron is likely to be found if we were to look. We do
not a path of movement), but rather a description of the not think of the electron moving in these patterns; they
probability of the position of the electron. simply describe probabilities. The drawings of the
The orbitals are the final pieces in our puzzle of the orbitals do not display the fact that they do not have
atom. Whenever we “look” at an electron (including sharp boundaries. The diagrams in Figure 17.4 show
looking with instruments), the electron reveals itself as the three types of orbitals by indicating the “skin” that
a particle. When we don’t look, the only knowledge we encloses the volume inside which the electron will be
have about the electron is what is contained in its found 90 percent of the time. Within the spherical s-
probability wave (or, to be more precise, “wave func- orbital, the electron is far more likely to be found near
tion”). Thus, when the electron exists in the unobserved the center than near the skin. Electron probability is not
atom, we cannot think of it as a charged particle moving evenly distributed in the other two orbitals either.
in a well-defined orbit. All that exists is the orbital, i.e., Discussing the size of an atom becomes difficult
a standing wave of probability satisfying the because there is really no outer boundary beyond which
Schrödinger equation. We are then freed from the prob- the electron can never be found.
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- Figure 17.4. Shapes of three orbitals: s-orbital (spher-
us where an atomic electron could be expected. This ical), p-orbital (three-dimensional dumbbell), d-orbital
electron cloud is a mental constraint, not a physical real- (rounded cloverleaf).
ity. The cloud is dense in some places and not so dense
in others, particularly as we recede from the nucleus. There is also a technicality, called the Exclusion
The density of the cloud near a point in space around the Principle, that does not allow more than two electrons
nucleus can be thought of as being proportional to the to exist in orbitals which occupy exactly the same space
probability of finding the electron there. At large dis- at the same time. In those cases where two electrons
tances from the nucleus, the probability gets very low, existing as orbitals try to occupy the same space at the
so the cloud gets very thin, but it never quite fades into same time, the electrons must differ in a characteristic
nothing. The solution of the Schrödinger equation called “spin,” a characteristic that is similar to the spin-
yields the numbers that represent the density of this ning of a ball on its axis. The spinning of electrons can
cloud for all points in space. For most atoms other than be referred to in two ways, either as “spin up” or “spin

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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

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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 Figure 17.8. Energies of the s and p orbitals for a mag-
energy. So we can have up to six electrons in an atom nesium atom.
in a triplet of p-orbitals with essentially the same ener-
gy. The d-orbitals come in a quintuplet of shape-orien- An electrically neutral magnesium atom will have
tation combinations. We can have up to ten electrons in just as many electrons as protons (both given by the
an atom in a quintuplet of d-orbitals with basically the atomic number). The electrons will be found in the low-
same energy. est-energy orbitals available and will pair up in sets of
Let us summarize what has been said about the two (spin up, spin down) if necessary. Many vacant
orbitals of a single atom such as magnesium (see Fig. orbitals of higher energy will remain. Absorbed light or
17.8). The s-orbitals are spherical; 1s is always the low- collisions with other atoms or particles can cause low-
est energy orbital, and 2s is the next lowest energy lying electrons to be excited to the higher energy vacant
orbital. The p-orbitals are shaped like dumbbells and orbitals, or even to leave the atom entirely (ionization).
the lowest energy of these is the 2p; it has energy just In each unit of time there is some probability that the
greater than that of the 2s orbital. The 3s orbital has the electron will spontaneously return to any vacancy avail-
next highest energy after the 2p orbital, and so on. 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, mixtures of a least two metallic elements: brass (copper
one of the possibilities becomes reality and the electron and zinc); solder (lead and tin); and the gold in jewelry,
jumps. In doing so it emits light, and this accounts for which has had silver or copper added to harden it.
observed emission line spectra. Some common nonmetallic elements are carbon in
the form of charcoal, graphite, or diamond; nitrogen and
Chemical Elements oxygen (gases comprising over 90 percent of the air we
breathe); and sulfur, a yellow substance.
Historically, the development of a model of atoms The names of the elements are listed in Appendix
came quite late. Long before the physicists had worked B. Notice that each element has its own symbol, which
out the details of atomic structure, chemists were work- is usually an abbreviation of its name. For example,
ing with things they too called “atoms.” However, the hydrogen is H, helium is He, and so forth. Some ele-
definition of “atoms” was not clear. For example, if ments have symbols that are based on their Latin names:
there were things called “atoms” it was quite possible sodium (natrium) is Na and potassium (kalium) is K.
that all substances (gold, hydrogen, carbon, and others) People working with the symbols of the chemical
were made of identical atoms that somehow combined elements sometimes add to an element’s symbol with
in different ways to create the different chemical char- numerical subscripts and superscripts indicating how
acteristics of the substances. If there were different many of the atomic building blocks are present in a par-
atoms for different substances, then it was quite feasible ticular atom. The atomic number is the number of pro-
that the atoms of a given substance were nevertheless tons in the atom and is usually written low and in front
different in size. If each substance had atoms of con- of the symbol: 1H, 2He, 6C. The mass number is the
sistent size, there was still no way to tell whether that number of nucleons (neutrons + protons) in the nucleus.
size was large or small. It was possible that the atoms It is approximately equal to the atomic mass expressed
were fluffy things like tufts of wool, which were in in atomic mass units (amu) (see Appendix B). The mass
physical contact. It was also possible that they were number is usually (but not always) written higher up
much smaller things that moved about in chaotic motion and in front of the symbol: 1H, 4He, 3He. Notice that
and only came in contact by collision. These theories two atoms of the same element (helium in this case)
had to be resolved by clever people throughout the cen- may have different mass numbers because, within lim-
turies. its, they may have different numbers of neutrons.
Robert Boyle is credited with giving us the modern A superscript following the symbol is often used to
idea of an element in the year 1661. He said an element designate the excess or deficiency of electrons com-
is any substance that cannot be separated into different pared to the neutral atom. A neutral helium atom could
components by any known methods. John Dalton made be written He0, but the 0 is usually left off neutral atoms.
the connection much later (ca. 1803) between elements If the atom has an extra electron it will have a negative
and atoms. He took the atoms of a particular substance charge, and the resulting ion will be designated He1–.
to be identical and defined an element to be a substance On the other hand, if helium loses an electron, it will
composed of only one kind of atom. have a positive charge and be represented by He1+.
Today, the atoms are modeled with Schrödinger’s Helium could lose both its electrons and be He2+. It
equation. Each time an additional positive charge (pro- would then be an alpha particle, the particle Rutherford
ton) is added to the nucleus, the equation predicts used to probe the atom and discover the nucleus. When
orbitals with new energy levels that are unique to the it is required, the symbol can be given numbers in all
number of protons used in the nucleus. Thus, today we three positions: 42He2+.
define an element to be: a group of atoms all having the
same number of protons. Summary
It is also important to note what has been left out of
this definition. Electrons were left out because one (or Orbitals are standing waves of electron probability
a few) can be removed easily and just as easily replaced established in the atom in a way specified by
from moment to moment. Mass was left out because it Schrödinger’s equation. Each orbital corresponds to a
depends on the number of nucleons in the nucleus specific energy that the electron has when it occupies
(including neutrons), and the number of neutrons may the orbital. The orbital patterns are discrete and so are
vary from nucleus to nucleus of an element despite the the energies associated with them.
fact that the number of protons does not. Electrons in an atom can be thought of as being in
You are no doubt familiar with some of the more a kind of energy well. They have less energy while in
than 100 known chemical elements. Most of the com- an atom than they have when they are free of the atom.
mon metals are elements: copper, tin, aluminum, and To free an electron from an atom (ionization), we must
nickel. Steel is nearly pure elemental iron, but it contains supply enough energy to remove it from its well.
small amounts of other metals and carbon. Alloys are A chemical element is a group of atoms all having

159
the same number of protons. Schrödinger’s equation 6. Node: The positions of destructive interference in
predicts different energy levels for atoms with different a standing wave. For waves in a one-dimensional
numbers of protons in the nucleus. This happens medium, such as a violin string, the nodes are
because differing amounts of charge on the nucleus points on the string that are not vibrating.
exert differing strengths of electromagnetic interaction 7. Orbit: See Chapter 15.
with the electrons of the atom. Thus, for each chemical 8. Orbital: A standing wave pattern of the probabili-
element there is a unique atom with its own characteris- ty waves which describe electrons in an atom.
tic energy levels. 9. Orbital Energy: The discrete energy that an elec-
tron has when it is described by a particular orbital.
STUDY GUIDE 10. Probability Wave: See Chapter 16.
Chapter 17: The Wave Model of the Atom 11. Shell: A grouping of energy levels within an atom.
Electrons having orbital energies within this group-
A. FUNDAMENTAL PRINCIPLES ing are said to belong to the same shell.
1. The Wave-Particle Duality of Matter and 12. Spin: A characteristic of electrons which has some
Electromagnetic Radiation: See Chapters 14 and similarity to the spinning of a ball on an axis
16. through its center. For an electron, however, there
2. The Exclusion Principle: No more than two elec- are only two possible ways of “spinning.” One is
trons may occupy orbitals that occupy the same called “spin-up” and the other “spin-down.”
space at the same time. Two electrons which do 13. Standing Wave: A pattern of constructive and
occupy the same orbital must differ in their spin. destructive interference of waves for which the
positions of constructive and destructive interfer-
B. MODELS, IDEAS, QUESTIONS, OR APPLICA- ence do not move.
TIONS
1. The Wave Model of the Atom: That model of the D. FOCUS QUESTIONS
atom in which the electrons are described by 1. What is a standing wave? What is an orbital? (What
orbitals, i.e., standing probability waves. In the is the connection between a standing wave and an
Wave Model of the Atom, the electrons in the atom orbital?) Why are only certain orbitals available in
have discrete energies and obey the Exclusion an atom? Describe the energy changes that occur
Principle. when an electron associated with one orbital goes
2. What are standing waves? to a different orbital.
3. What are standing waves of probability? 2. Carefully outline the main elements of the Wave
4. Why are only certain “orbitals” allowed? Model of the Atom. Draw a simple energy well
5. What is an “unwatched” electron doing? representing an atom. What do the horizontal lines
6. How many electrons can be associated with a sin- in the energy well figure represent? Describe what
gle orbital? happens to the energy of an electron when it moves
7. How is an electron in an atom classified or given an and is then associated with an orbital higher in the
“address?” energy well.
8. What is an energy well?
E. EXERCISES
C. GLOSSARY 17.1. Does Figure 17.4 depict surfaces on which the
1. Antinode: The positions of constructive interfer- electron in an atom travels? If not, what do the surfaces
ence in a standing wave. On a violin string, the represent?
antinodes are the positions of maximum vibration
of the string. 17.2. What scientific principle suggests that it is
2. Atomic Number: The number of protons in an impossible to know simultaneously both the position
atom. and velocity of an electron in an atom?
3. Chemical Element: A substance consisting of
atoms, all of which have the same number of pro- 17.3. Which of the letters—s, p, d, or f—designates
tons. an orbital shaped like a rounded, four-lobed cloverleaf?
4. Energy Well: A conceptual model for visualizing
the discrete energies of electrons in an atom. 17.4. Why can’t an electron remain at a fixed posi-
Electrons within an atom have less energy than tion outside the nucleus?
they have when free of the atom, much like a ball
which has fallen into a well. 17.5. Why can’t an electron revolve indefinitely
5. Mass Number: The combined number of protons around the nucleus in orbit?
and neutrons in the nucleus of an atom.

160
17.6. If an electron is in a spherically shaped orbital 17.13. Which element has the same number of elec-
(e.g., Fig. 17.4), is it possible for the electron sometimes trons in an s-orbital as beryllium, Be?
to be outside the spherical skin?
17.14. Which element has the same number of elec-
17.7. Is there any possibility that an electron from trons in a p-orbital as boron, B?
an atom in this paper could be on Mars for a moment
today? 17.15. The atomic number of nitrogen is 7. How
many electrons does one of its atoms have? How many
17.8. Draw a diagram like Figure 17.5 showing protons? How many neutrons? State the pattern or rela-
only 1s, 2s, 2p, and 3s orbitals (all unfilled). Put in tionship among these numbers and check to see if all of
enough electrons to represent Li. Note the single elec- the other atoms in Table 17.1 follow this pattern.
tron in the 2s orbital. A similar element should have the
orbitals filled until there is one electron in the 3s orbital. 17.16. If you know how many protons an atom has,
How many more electrons are required to fill orbitals what else must you know to calculate its mass number?
until there is one electron in 3s? What neutral element
has this many electrons? 17.17. Use Table 17.1 or Appendix B when neces-
sary to complete Table 17.2.
17.9. A neon sign is simply a glass tube filled with
neon gas. When electricity is passed through, it 17.18. Use Appendix B to decide which of the fol-
becomes a discharge tube. The electrons in the neon lowing are elements:
atoms are raised to higher levels. Explain why the tube (a) lead
then glows red and why, if the tube is filled with xenon (b) arsenic
gas, different colors are emitted. (c) bronze
(d) radon
17.10. Which atoms in Figure 17.7 have filled (e) potash
shells? Which have unfilled shells? Would more ener- (f) platinum
gy be required to remove the highest energy electron in (g) mercury
a filled shell or an unfilled shell? (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+

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