Chemistry 482

Homework Set #4
Due Feb. 22, 2013


1. A particle confined to a 1-D box of length a has the wavefunction:
{
a. Make a sketch of the particle-in-a-box potential and this wavefunction.
b. Determine the Constant A needed to normalize the wavefunction.
c. If you make one energy measurement on one particle, what is the probability that you will measure
this average energy? Provide a brief explanation of your answer.

2. Suppose that the wavefunction for a system can be written as
1 2 3
1 1 3 2
( ) ( ) ( ) ( ),
2 4 4
i
x x x x
+
= + +
where |1(x), |2 (x) and |3 (x) are normalized eigenfuctions of the kinetic energy operator

T with
eignevalues E1, 3E1, and 7E1, respectively.

a. Verify that ) (x is normalized.
b. What are the possible values that you could obtain in measuring the kinetic energy on this system?
c. What is the probability of measuring each of these eigenvalues?
d. If you were to perform a large number of measurements of the kinetic energy for this system, what
average value would you obtain?


3. For the simple harmonic oscillator determine:

a.

[ , ] H x b.

[ , ] T V
c.

T V and for the harmonic oscillator eigenstate
2
1/4
3
2
1
4
( ) ,
x
k
x xe
o
o
o
t
| |
= =
|
\ .
where


4. In the infrared spectrum of Li
7
H
1
there is an intense line at 1406.6 cm
-1

a. Determine the force constant k in units of N/m and in units of dyn/cm (1 dyn = 1 gcm/s)
b. Find the rms (root mean square) displacement of Li
7
H
1
in the ground state, for which =159.5 pm
c. Compare the rms displacement to . By what percentage is the bond compressed?

( ) 0 / 2
( ) ( ) / 2
x Ax x a
x A a x a x a

= s s
= s s
for
for
2
v. =- 0
v:::: co
(b) tVurmcJilxtioYJ
'\0 11r* , aft 1
f 0 0/ ('X) l{F ex) x:::
a. r.l ,
f
- J -tit' f
V
\ 'l/' "I.lf- 71r j 1
. ~ /f(f)f) L/1('X) c;if)d + ~ ~(?4) 1(?() {AX =
(A rIA
S; A:l9(? Jx + Jt A2 (rA-ex/ J?( = I
]1 ().3 .2.( 2(). . It" I 3z_
A "-~ (z:) + A Q 2 + a ~ a - 1~ - 4a ) - (
i-A2(l= I
~ A= T/2
-7 ~J(fJ
(e) To -rnd (f> , 901fe~ toke Ip;tt~I'N <[>" fo,i.fi~H r ole
if We s1(l11fi~Me {n.i~foJ ~ 0 D
J
ll *2 dt ('" ~oI' -
':E> == ; rjg; X) (- 2m fi) iff, -x ) d?t + l~,[g; (o.-vf-ld~ )j(a-xJd,
we 0bt~() < E- > =0 , l+,{l; Vic{aie U!J certaJ1 6nd -fAj, oJso
Ulolccte pvsiuh-te 3 (rrM~t meCt5ure e~e,nuVues)
.' lt1D tro~olJi'Utfet7 1- meosurJ~ <E>=O
~ vi' cJ Nete : /?x? cause 1:- (s not con;t 111ilOU s @ x", ~ ,the a vtucJ
irU~ 1- [lJriN;;h: ~'; Sfectal h~,J11'nU
Fur. mlAi0, crfiCi'fJI)ado bRAe is what 1'5 nmded 10 -treat #.e J~.
-
-
e13
erw
Ov/ /Aeh 1- eJJ~ ~ .
H~kr8 UfIcerin.!'n1y
(?A'S eJIIJcJ i,{ e.s /
Su < E> ':0 ~!dfJe6n't- Violate
bvLt IT 51Jr'11 fsn~ one 01 ~
PNJbOvbIU~ I~ Si1'/I ~e10
:2
b.
o.
-Jir = .ltD I 10 ,.j2-}'
'f ['X) .2.'11(1)() t 4,:)(rx)+ 4- tp3l~)
J-o/:) tfc'X) cix =- J [t p~'X) t Ii r~'X) + +if(.(?(} ] 0/",
/\
(redA'3e -the ei6e1ltnctPn5 ~ T rw Dr~~ here)
J
'1fr~ 11(" ..~ - r J ::2 .L . S' I ~ . I /1 2. AI
~ (~) 'f (~) C{~ - J 41j71 ('/()(}.?(T Iblf/:z ('X)d~ + 16 fa (tX)()f X
- 1..J.......L..J-lL - I
-f" 16 I 16 -
(reoJAi eLlen e{{rfunctfon /5 rorma1J~ here)
The un~ po$ible ualue!.> VU1LIoI' obto.ln is E" af3./ OJlJ 1E.1
which ()i'e ~ eI'aer;xJlAw 1eaen @jenf'lMlctton
G
FOT
G,
P = (v = i
)'
For ?:E I
I
p= (f)2= tc:
fur 1E/
1)=
( ..9W l' ) ( 3-,M _ ..!.L
I
4- 4-) - tZ;
d <T>::: P, TI + P2. T.2 -+ P3 T3
_ .-l r +- .L?r t 1L.:J..r - 1!LE.- 2./ E
4- . C-,. Ih Jt:. ) if? I c r - 16 I - T I
3.
.2 -2
== /-0/8 x /0 k,g s
2 /0-000 ern I
- {,of8 x [0 f~8 I k tl 'em '5<-
= f.O I ~ X fO 5 3 f! S -2 = {'o/8' X/rF d!jn /0ffJ
-II
- /-'tXrO m=/f.fpm
(c)
t,335Jo