SECTION 3.

7 Quantum Numbers

79

SECTION 3.6 REVIEW

Quantum Mechanics
3.6.1

What is the minimum uncertainty in the position of an electron moving at a speed of

4 106 m/s 1 percent? (The mass of an electron is 9.11 1031 kg.)

3.6.2

What is the minimum uncertainty in the position of a proton moving at a speed of

4 106 m/s 1 percent? (The mass of a proton is 1.67 1027 kg.)

3.7 QUANTUM NUMBERS

In Bohrs model of the hydrogen atom, only one number, n, was necessary to describe the location
of the electron. In quantum mechanics, three quantum numbers are required to describe the distribution of electron density in an atom. These numbers are derived from the mathematical solution
of Schrdingers equation for the hydrogen atom. They are called the principal quantum number,
the angular momentum quantum number, and the magnetic quantum number. Each atomic orbital
in an atom is characterized by a unique set of these three quantum numbers.

Student Annotation: The three quantum

numbers n, , and m specify the size,
shape, and orientation of an orbital,
respectively.

Principal Quantum Number (n)

The principal quantum number (n) designates the size of the orbital. The larger n is, the greater
the average distance of an electron in the orbital from the nucleus and therefore the larger the
orbital. The principal quantum number can have integral values of 1, 2, 3, and so forth, and it corresponds to the quantum number in Bohrs model of the hydrogen atom. Recall from Equation 3.7
that in a hydrogen atom, the value of n determines the energy of an orbital. (As we will see shortly,
this is not the case for an atom that contains more than one electron.)

Angular Momentum Quantum Number ()

The angular momentum quantum number () describes the shape of the atomic orbital [ Section
3.8]. The values of are integers that depend on the value of the principal quantum number, n. For a
given value of n, the possible values of range from 0 to n 1. If n = 1, there is only one possible
value of ; that is, 0 (n 1 where n = 1). If n = 2, there are two values of : 0 and 1. If n = 3, there
are three values of : 0, 1, and 2. The value of is designated by the letters s, p, d, and f as follows:14

Orbital designation

Thus, if = 0, we have an s orbital; if = 1, we have a p orbital; and so on.

A collection of orbitals with the same value of n is frequently called a shell. One or more
orbitals with the same n and values are referred to as a subshell. For example, the shell designated
by n = 2 is composed of two subshells: = 0 and = 1 (the allowed values for n = 2). These
subshells are called the 2s and 2p subshells where 2 denotes the value of n, and s and p denote the
values of .

Magnetic Quantum Number (m)

The magnetic quantum number (m ) describes the orientation of the orbital in space [ Section 3.8]. Within a subshell, the value of m depends on the value of . For a certain value of ,
there are (2 + 1) integral values of m as follows:
, ... 0,... +
The unusual sequence of letters (s, p, d, and f) has an historical origin. Physicists who studied atomic emission spectra tried to correlate
their observations of spectral lines with the energy states involved in the transitions. They described the emission lines as sharp, principal,
diffuse, and fundamental.
14

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80

CHAPTER 3 Quantum Theory and the Electronic Structure of Atoms

TAB L E 3 . 2

Allowed Values of the Quantum Numbers n, , and m

When n is

can be

When is

m can be

only 0

0 or 1

0, 1, or 2

0, 1, 2, or 3

0
0
1
0
1
2
0
1
2
3

only 0
only 0
1, 0, or +1
only 0
1, 0, or +1
2, 1, 0, +1, or +2
only 0
1, 0, or +1
2, 1, 0, +1, or +2
3, 2, 1, 0, +1, +2, or +3

=3
=2
=1
=0

+1

2 1

+1 +2

+1

3 2 1

+1 +2 +3 = 3 f subshell

2 1

+1 +2

= 2 d subshell

+1

= 1 p subshell

n=1

n=2

n=3

n=4

= 0 s subshell

Figure 3.15 Illustration of how quantum numbers designate shells, subshells, and orbitals.
If = 0, there is only one possible value of m: 0. If = 1, then there are three values of m: 1, 0,
and +1. If = 2, there are five values of m, namely, 2, 1, 0, +1, and +2, and so on. The number
of m values indicates the number of orbitals in a subshell with a particular value; that is, each
m value refers to a different orbital.
Table 3.2 summarizes the allowed values of the three quantum numbers, n, , and m, and
Figure 3.15 illustrates schematically how the allowed values of quantum numbers give rise to the
number of subshells and orbitals in each shell of an atom. The number of subshells in a shell is
equal to n, and the number of orbitals in a shell is equal to n2.
Worked Example 3.8 gives you some practice with the allowed values of quantum numbers.

Worked Example 3.8

What are the possible values for the magnetic quantum number (m) when the principal quantum
number (n) is 3 and the angular momentum quantum number () is 1?

Strategy Use the rules governing the allowed values of m. Recall that the possible values of m
depend on the value of , not on the value of n.

Setup The possible values of m are ,..., 0,..., +.

Solution The possible values of m are 1, 0, and +1.
Think About It

Consult Table 3.2 to make sure your answer is correct. Table 3.2 confirms that it is the value of , not
the value of n, that determines the possible values of m.
Practice Problem A What are the possible values for m when the principal quantum number (n) is 2
and the angular momentum quantum number () is 0?
Practice Problem B What are the possible values for m when the principal quantum number (n) is 3
and the angular momentum quantum number () is 2?

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Quantum Numbers
Pauli Exclusion Principle: no two electrons can have the
same set of four quantum numbers
1st - Principle QN

2nd - Orbital QN

3rd - Magnetic QN

4th - Spin QN

ml

ms

l goes from 0 to n-1 within an

energy level
n = 1,2,3...7

l values = 0 (for s), 1(for p), 2 (for

d), 3 (for f) sublevels

Values of ml go from +l to - l ,
which gives 2l+ 1 number of
values

has 2 values:
+1/2 (spin up) and -1/2(spin
down)

1. measures the average

distance of the e- from the
nucleus

1. indicates the shape of the

orbital ( set of probable locations
of the e- )

1. identifies the direction the eorbital has around the nucleus

1. identifies the "spin"

or rotation of the e- about its
own axis

2. different values of n mean

different energy levels

2. diff. values of l mean diff

sublevels. In a sublevel all the ehave nearly the same energy.

2. specifies the e- orbital in

which the e- is located within a
sublevel.

2. shows that each orbital can

contain only 2 e-

3. different values of n mean

relatively large differences in the
energies of the e-s

3. different sublevels within the

same level may have moderately
large differences in energy.

3. different values of ml mean

little difference in energies of
the e-

3. the direction of spin is either

in one direction or the other

4. the smallest average distance

and the lowest energy occurs
when n = 1; each increase in n
increases those quantities.

4. within any level, the lowest

energy sublevel is s, then p, then
d, then f.

4. the number of possible

values of ml within a sublevel
identities how many e- pairs
that the sublevel can hold

4. when 2 e- (in an atom) have

the same set of QN except for
ms, then these e-are called an epair

5. the number of e- possible in a

level is 2n2

5. the number of possible values

of l for a level is equal to the value
of n

5.these e- within an e- pair have

essentially the same energy