Chem 6, 9 Section

Spring 2002

Assignment 4 Solutions
1. The red line in the Balmer series is the photon that results when the H atom changes
state from n = 3 to n = 2. This photon has an energy

Ephot = E3 E2 =

2.18 1018 J
32

2.18 1018 J
22

= 3.03 1019 J .

This is the energy that the electron in the box will gain when it absorbs the photon. The
electron starts in its ground state (n = 1, where this n is the particle-in-a-box quantum
numberthe other n is the H atom principal quantum number), absorbs this energy, and
ends in n = 2. This energy change is related to the box length L through
E =

h 2 22 12
8meL 2

or

L=

3h 2 = 7.73 1010 m = 7.73 .

8me E

2. Problem 77 makes it clear that the symmetry of the wavefunction ensures that the
probability of finding the particle between 0 and L/4 is 1/4, as the figure below emphasizes.
2

n=2

x/L
The area under the red curve for 2 over the interval 0 x L/4 (the green bar) is the same
as the area over L/4 x L/2 or L/2 x 3L/4 or 3L/4 x L. But for n = 1, the
symmetry changes:
2

n=1

x/L

Chem 6, 9 Section

Spring 2002

Here, you can see at a glance that the area under 2 from 0 to L/4 is much less than the
area from L/4 to L/2. Thus, the probability of finding the particle anywhere between 0 and
L/4 is much less than the probability of finding it between L/4 and L/2. (Note however that
symmetry can still be invoked here for some situations. The probability between 0 and L/4
is the same as from 3L/4 to L, for instance.) The probabilitys numerical value in this case
is given by the expression below (and I dont expect you to know how to do this integral
off the top of your head!):
L/4

L/4

(x)2

Probability =
0

dx = 2
L 0

sin2

x
2
dx =
= 0.0908 .
L
4

3. First, we use the expression in Equation [15.22] to calculate the size of a hydrogen
atom (Z = 1) in the 3d (n = 3, l = 2) state:
r nl =

n 2a0
l (l + 1)
1+1 1
= 10.5 a0 .
Z
2
n2

Then we make a table of r nl values for various n and l values for He+ (Z = 2):
n
1
2
2
3
3
3
4
4
4
4
5
5
5
5
5

l
0
0
1
0
1
2
0
1
2
3
0
1
2
3
4

r nl /a0
0.75
3.00
2.50
6.75
6.25
5.25
12.00
11.50
10.50
9.00
18.75
18.25
17.25
15.75
13.75

This table shows that the n = 4, l = 2 (or 4d) He+ ion has the same average size as the H
atom in the 3d state. The He+ 4s and 4p states and all n > 4 states are larger than H 3d.
Note as well that the average radius does not depend on the m quantum number.
4. First, lets review the Zeff calculation. We know the Na first ionization energy: IE =
8.23 1019 J, and we measured the sodium D line wavelength in lab to be about = 590
nm. This wavelength corresponds to a photon energy of

Chem 6, 9 Section

Spring 2002

Ephot = hc = 3.37 1019 J .

We can now construct the energy level diagram below for Na:
E=0

n=

0J

E3p = IE + Ephot
4.95 1019 J

3p

Ephot
E3s = IE

3s

8.23 1019 J
From the general expression for the energy of an atomic level in terms of an effective
nuclear charge:
2
2
Zeff,n,l
e 4me Zeff,n,l
18
En,l =
= 2.18 10
J
n2
820 h 2 n 2

we can write an expression for Zeff:

Zeff,n,l =

n 2 En,l
2.18 1018 J

Our level energies for these two n = 3 levels give

Zeff 3s =
Zeff 3p =

32 E3s
2.18 1018 J
32 E3p
2.18 1018 J

32 (8.32 1019 J)

2.18 1018 J

32 (4.95 1019 J)
2.18 1018 J

= 1.85

= 1.43

Now we can use Equation [15.25] to calculate average radii for these two orbitals:

Chem 6, 9 Section

Spring 2002

n 2 a0
l(l + 1)
1+1 1
Zeff
2
n2
2
3 a0
0(0 + 1)
r 3s =
1+1 1
= 7.30 a0
1.85
2
32
r nl =

r 3p =

32 a0
1(1 + 1)
1+1 1
= 8.74 a0
1.43
2
32

Now we can move on to Cs. The analogous transition in Cs involves n = 6 instead of n =

3 levels. The Cs atom changes configuration from [Xe]6p1 to [Xe]6s1. The 873.5 nm
photon that is emitted in this change has an energy Ephot = 2.27 1019 J, and with a
6.24 1019 J ionization energy, our energy level diagram looks like this:
E=0

n=

0J

E6p = IE + Ephot
3.97 1019 J

6p

Ephot
E6s = IE

6s

6.24 1019 J
Repeating the effective nuclear charge calculation (with n = 6) gives Zeff = 3.21 for the 6s
level and 2.56 for the 6p level.