Chapter 7/A Quantum Mechanical Model for the Vibration and Rotation of Molecules

7-16
P7.21) By substituting in the Schrdinger equation for rotation in three dimensions,
show that the rotational wave function
( )
1/ 2
2
5
3cos 1
16

| |

|
\ .
is an eigenfunction of the
total energy operator. Determine the energy eigenvalue.

( ) ( )
( )
( ) ( )
2
2
2 2 2
0
1/ 2 1/ 2
2 2 2
2
2 2 2
0
2
2
0
, ,
1 1
sin ,
2 sin sin
5 5
3cos 1 3cos 1
16 16
1 1
sin
2 sin sin
5
2 16
Y Y
EY
r
r
r

( | |
+ =
( |

\ .
( | |
| | | |
( |
` ` | |
\ . \ . ( |
) )
+
( |

( |
| (
\ .
|
=
=
=
=
( ) ( ) ( )
{ } ( ) ( ) ( )
1/ 2 1/ 2
2
2 3 2
2
0
1/ 2 1/ 2 1/ 2
2 2 2
2 2 2 2
2 2 2
0 0 0
1 5 1
6cos sin 6sin 12cos sin
sin 2 16 sin
5 5 6 5
6 1 cos 12cos 6 18cos 3cos 1
2 16 2 16 2 16
The energy
r
r r r

| ( | | (
=
| |
( (

\ . \ .
| | | | | |
( (
= = =
| | |

\ . \ . \ .
=
= = =
2 2
2
0
3
eigenvalue is , corresponding to ( 1) with = 2.
2
l
E l l l
r I
= +
= =

P7.22) Show by carrying out the necessary integration that the eigenfunctions of the
Schrdinger equation for rotation in two dimensions,
1
2
1
2

e e m n
im in
l l
l l
and ,

are orthogonal.
1
2
2 1 2 0
2
0
2
0
2

F
H
G
I
K
J
= +
= + =

z z
e e d m n i m n d
m n i m n
m n
im in
l l l l
l l l l
l l
l l

1
2
1
2
because is an integer
cos sin
cos sin
b g b g c h
b g b g c h
b g


P7.23) In this problem you will derive the commutator

, .
x y z
l l i l
(
=

=
a) The angular momentum vector in three dimensions has the form
x y z
l l l = + + l i j k
where the unit vectors in the x, y, and z directions are denoted by , , and i j k.
Determine l
x
, l
y
, and l
z
by expanding the 3 3 cross product l r p. = The vectors
and r p are given by r k x y z = + + i j and .
x y z
p p p = + + p i j k
b) Substitute the operators for position and momentum in your expressions for l
x
and l
y
.
Always write the position operator to the left of the momentum operator in a simple
product of the two.
c) Show that

, .
x y z
l l i l
(
=

=
Chapter 7/A Quantum Mechanical Model for the Vibration and Rotation of Molecules

7-20
( )
( ) ( )
( ) ,
,
d f df
i f i i i f
d d
i i

(
(

= + =
(

(
=
(

= = = =
= =

Because the commutator is not equal to zero, it is not possible to simultaneously know
the angular orientation of a molecule rotating in a two-dimensional space and its angular
momentum.

P7.29) At 300 K, most molecules are in their ground vibrational state. Is this also true
for their rotational degree of freedom? Calculate
1 5
0 0
and
J J
J J
n n
n n
= =
= =
for the H
35
Cl molecule
whose bond length is 1.2710
10
m. Make sure that you take the degeneracy of the
levels into account.
( )
( ) ( )
( )
( )
2
2
1
-
2 1
0
2
34
2
27 1 10 23 1
1
0
1
-
2 5
0
2 1
= e
1
1.055 10 J s 1 1+1
3 exp
1.0078 34.9688
2 amu 1.66 10 kgamu 1.27 10 m 1.381 10 J K 300 K
1.0078 + 34.9688
= 2.708
2 1
= e
1
J J
I kT J
J
J
J
J J
I kT J
J
n J
n
n
n
n J
n
+
=
=

=
=
+
=
=
+
(
(

= (

(

(

+
=
=
=
( ) ( )
( )
2
34
2
27 1 10 23 1
5
0
1.055 10 J s 5 5+1
11 exp
1.0078 34.9688
2 amu 1.66x10 kgamu 1.27 10 m 1.381 10 JK 300 K
1.0078 +34.9688
= 2.369
J
J
n
n

=
=
(
(

(

(


P7.30) Draw a picture (to scale) showing all angular momentum cones consistent with
l = 5. Calculate the half angles for each of the cones.

Chapter 7/A Quantum Mechanical Model for the Vibration and Rotation of Molecules

7-21
m
l
= +5
m
l
= +4
m
l
= +3
m
l
= +2
m
l
= +1
m
l
= 0
m
l
= -1
m
l
= -2
m
l
= -3
m
l
= -4
m
l
= -5

The half angles of the cones measured from the positive and negative z axis are
( )
1
5
5
cos 0.420radians
5 5 1
l
m

=
| |
| = =
|
+
\ .

( )
1
4
4
cos 0.752 radians
5 5 1
l
m

=
| |
| = =
|
+
\ .

( )
1
3
3
cos 0.991radians
5 5 1
l
m

=
| |
| = =
|
+
\ .

( )
1
2
2
cos 1.20radians
5 5 1
l
m

=
| |
| = =
|
+
\ .

( )
1
1
1
cos 1.39 radians
5 5 1
l
m

=
| |
| = =
|
+
\ .

( )
1
0
0
cos 1.57 radians
5 5 1
l
m

=
| |
| = =
|
+
\ .

as well as minus these values for the negative values of m
l
.