Chemistry 482

Homework Set #5
Due Mar 13, 2013


1. Consider the wavefunction ) 1 cos 3 (
16
5
) , (
2
2 / 1
|
.
|

\
|
= u
t
| u
a. Show that this function is an eigenfunction of the total energy operator for a rigid rotor

b. Show that this function is normalized over the interval t u s s 0 and t | 2 0 s s


2. The moment of inertia of
1
H
35
Cl is I=2.644 x 10
-47
kg m
2
.

a. Calculate Erot/kBT for J =0,5,10, and 20 at 298 K

b. For which of these values of J is Erot/kBT ~ 1?


3. A rigid rotor is described by the wavefunction
( ) ( ) ( )
1,1 2,0 3,0
1
( , ) , 2 ( , 3 ( ,
14
Y Y i Y u | u | u | u |
(
= + +

, where ( )
,
,
m
Y u | are the spherical harmonics with
the total angular momentum quantum number and the magnetic quantum number m.

a. If Lz is measured for this system, what are the possible values that will be observed and what is the
probability for each value?

b. If the magnitude of angular momentum, L , is measured for this rigid rotor, what are the possible
values that will be observed and what is the probability for each value?


4. Consider a rigid rotor which has 2 = as one of its quantum numbers.
a. What are the possible angles between L

and the z axis for this rigid rotor?

b. What are the possible eignevalues of the operators (if any) for
2 2 2 2
, , and
x y x y
L L L L + ?


5. Find the most probable angles and u | for a particle described by the rigid rotor wavefunction
( )
3
, sin
8
i
Y e
|
u | u
t

=
#5
b. S: sillll de \~; Jf ff (o!OBcSTL, 0 ~o/s; 2fC )
_ 21' I~Sine d fj (k) ( 3CVS6 -/ t = :11t r:(-rSr ) ( qCOS~s/ nfI - 6 COlOs!'r1l7 +sinfl)d
= tJ: (9C:eS1ne - 6~sin9 +sine )Je
= -f[ q. +-6-+ + 2) = 1 (norma,{jied)
.2.
n:1
a. rcrl; = ..2I J(J +I )
.t,..a I
Erot (KaT::: ~ I<sT J (J +t)
_ (1.055)(Jo-
3
4- JS)~ J(J+{)
- 2.2.f;44-X 10- 4-i~.m:l. ,.3gX(O-~3J' k-
I
. 2q~I<'
- 0 . oS f J (J +I )
:. 0
::::15~
(J=o)
(J=5)
( .1=10)
(:r=2.o)
= !;.63
= .21.5D
b.
b. L~ N/A
LS N/A
2- ~ ;;. L2
Lx t L'J ::: L - c
.") 2
= 61T~ - Ll
Om:=. 0 1 ~ ~_~_' :x-:.....~-tJ-~ -_
/ -h 2 f -h<- m :::: } .:=: i 6 -t; '2. ( Tn ==0 -
f7fJ. 5--n
2
m-=)
4-~2 m =1-2 2tfz; til::- 2
\((9, ~)-o,g <;lnB e--J'~
p -= f~ r* r sfne elL ta ji'rki the most prohoJoJe (J / ~
dp _ dp _ dsm~ _ \ :2 _. 2-
\ ae -0 ale - dfl - 3smE! vose - 3(f- C{J)e) case =-0
I~-= 0 CQ;6= / 0/ w;(J =0 e= 0, !} ,7r
dcp ~ (r'n depeJ)cie;vt ) ~ == 0 ~ 2n
3.
a.
L i ::: mtr ( P-1Qa - l~q4-)
(,,1 =/ m=/ Ll= n
)2,0 l=2 m=- 0 Ll= D
13,0 t=-6 m= 0 L=I= 0
b ILl::: n('1 lUtl)
Y; J 1 l =-/ J LI = 12t
Y2,V ,{:= z. I L } = fbt
Y3/v ~ =-3 ILl == ~ TI-
t:=:2 m= 0/ /, ~
a. Ll:= m Pi =- 0I yf, 211
/L I =-nJU~+J) ::: JTn
4
I
p= 1t1~+?
t -Ii
J p:::- 14-
I
~Tt
!
p= If
p~t
P=#
m= f
m=-j
~.~ . ~=: .2j)
lin .
iL L e := 35: 3
0
2~~ (J-/4+.7-'
m=2
m.:::-2