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# CHEM 342. Spring 2002. Problem Set #2. Answers.

Orthogonality
1. Prove that the !n"tions
,
_

a
x
Asin
1
an#
,
_

a
x
A
2
sin
2
are orthogonal
( ) a x 0
.
Hint\$
( )
( )
( )
( )
C
m n
x m n
m n
x m n
mxdx nx +
+
+

2
sin
2
sin
sin sin
( ) ( )
( ) ( )
0
%
3 sin
2
sin
%
3
sin
2
sin
2
2
2
sin
2
2
2
sin
2
sin sin
2
sin sin
2
2
0
2
0
2
0 0
2
&
1

1
1
1
1
]
1

,
_

,
_

1
1
1
1
]
1

,
_

,
_

,
_

,
_

1
1
1
1
]
1

,
_

,
_

,
_

,
_

,
_

,
_

,
_

,
_

a a
A
a
a
a
a
a
a
A
a
x
a
a
x
a
A
dx
a
x
a
x
A dx
a
x
A
a
x
A dx
a
a a a
2. 'ive a mathemati"al #einition or the (ronne")er #elta
( )
nm

## . *hat is the n!meri"al

val!e o the (ronne")er #elta when the two eigen!n"tions are orthogonal+ *hat is the
n!meri"al val!e o the (ronne")er #elta when n an# m are the same eigen!n"tion ,i.e. n - m.+
/n a##ition to these two val!es0 "an the (ronne")er #elta be e1!al to an2 other n!meri"al val!es+

d
m n nm
&
3he eigen!n"tions n

an# m

## are orthogonal when

0
nm . 3he other possible val!e
o the (ronne")er #elta is 10 an# it o""!rs when n - m. 3he (ronne")er #elta "an onl2 e1!al 4ero
or one5 no other val!es are possible.
Operators
3. 6in# the res!lt o operating with

,
_

dy
d
y A
an#

,
_

dy
d
y B
on the !n"tion
( )
2 7
2
y
e y f

. /s ,2. an eigen!n"tion o
A
8
or o
B
8
+
( ) ( )
( ) ( )( )
( )
2 7
2 7 2 7
2 7 2 7
2
2 2
2 2
2
y
y y
y y
ye y f A
y e ye y f A
e
dy
d
ye y f A

3his !n"tion is not an eigen!n"tion o
A
8
.
1
CHEM 342. Spring 2002. Problem Set #2. Answers.
( ) ( )
( ) ( )( )
( )
( ) ( ) ( ) ( )
2 7 2 7
2 7 2 7
2 7 2 7
2 7 2 7
2 2
2 2
2 2
2 2
0
y y
y y
y y
y y
e e y y y f B
ye ye y f B
y e ye y f B
e
dy
d
ye y f B

+
+
3his !n"tion is an eigen!n"tion o
B
8
with eigenval!e o 4ero.
4. 6in# the ollowing "omm!tators or an2 !n"tion ,9..
,a.
1
1
]
1

2
0
8
x d
,b.
1
1
]
1

x d 8 0
2
Hint\$
dx
d
d
8
0
2
2
2
dx
d
d

0 x x 8 0 an# 2 2
x x

.
,a.
( ) ( ) ( )
( ) ( ) [ ]
( )
( ) ( )
( )
( )
( ) ( )
( ) [ ] ( ) x f x x f x d
x
dx
x df
dx
x df
x
dx
x d
x f x f x d
x
dx
x df
x f x
dx
d
x f x d
x f d x x f x d x f x d
2 0
8
0
8
0
8
8 8
0
8
2
2 2
2
2
2 2 2
2 2 2

1
1
]
1

,
_

+
1
1
]
1

,
_

1
1
]
1

1
1
]
1

3hereore
x x d 2 0
8
2

1
1
]
1

,b.
2
CHEM 342. Spring 2002. Problem Set #2. Answers.
( ) ( ) ( )
( ) ( ) [ ]
( )
( ) ( )
( ) ( )
( ) ( )
( ) ( )
( )
( ) ( ) ( ) ( )
( )
( ) ( )
( )
( )

,
_

1
1
]
1

+
1
1
]
1

+ +
1
1
]
1

1
]
1

+
1
1
]
1

1
]
1

+
1
1
]
1

1
1
]
1

1
1
]
1

dx
x df
x f x d
dx
x df
dx
x df
x f x d
dx
x f d
x
dx
x f d
x
dx
x df
dx
dx
dx
x df
x f x d
dx
x f d
x
dx
x df
x x f
dx
d
x f x d
dx
x f d
x
dx
x df
x
dx
dx
x f
dx
d
x f x d
dx
x f d
x x xf
dx
d
x f x d
x f d x x f x d x f x d
2 8 0
8 0
8 0
8 0
8 0
8 0
8 8 8 0
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2 2 2
3hereore

,
_

1
1
]
1

dx
d
x d 2 8 0
2
:. 6in# the res!lt o operating with the operator
r dr
d
r
dr
d
r
O
2 1
2
2
+
,
_

,
_

on the !n"tion
br
Ae

## . *hat val!es m!st the "onstants have or

to be an eigen!n"tion o

O
+
( ) ( ) ( )
( ) ( ) [ ] ( )
( ) ( ) [ ] { } ( )
( ) ( ) ( )
( ) ( )
( )
1
]
1

+
+
+
1
]
1

+
+ +
+

'

,
_

'

1
]
1

,
_

,
_

r r
b
b Ae Ae O
Ae
r r
Abe
e Ab Ae O
Ae
r r
e
be bA Ae O
Ae
r
re be r bA
r
Ae O
Ae
r
bAe r
dr
d
r
Ae O
Ae
r
Ae
dr
d
r
dr
d
r
Ae O
br br
br
br
br br
br
br
br br
br br br br
br br br
br br br
2 2
2 2
2 2
2
2
1
2 1
2 1
2
2
2
2
2
2
2
2
6or to be an eigen!n"tion o

O
0 the "onstant b m!st e1!al 10 while A "an be an2 real
n!mber. /n this "ase0 the eigenval!e is 1.
%. 6in# the res!lt o operating with the operator
2
on the !n"tion ( )
2 2 2
z y x + + . /s it an
eigen!n"tion+
3
CHEM 342. Spring 2002. Problem Set #2. Answers.
( ) [ ] [ ] [ ]
( ) [ ] [ ] [ ]
( )
( ) %
2 2 2
2 2 2
2 2 2 2
2 2 2 2
2 2 2 2
0
2 2 2
2
2
0
2 2 2
2
2
0
2 2 2
2
2
2 2 2 2
2
2
2
2
2
2
2
+ +
+ + + +

+ +
+ +

+ + +

+ + +

+ +

z y x
z y x
z
z
y
y
x
x
z y x
z y x
z
z y x
y
z y x
x
z y x
z y x
y x z x z y
3his is not an eigen!n"tion o
2
.
;. 3he !n"tion
( ) x Ax 1
is a well<behave# wave !n"tion in the interval 1 0 x .
Cal"!late the normali4ation "onstant ,A.0 an# the average val!e o a series o meas!rements o 9
,i.e in# the e9pe"tation val!e\$ > < x ..
( )
( )
( )
( )
30
1
30
1
1
:
1
4
1 2
3
1
1 2
1 2 1
1 1
1
2
: 4 3
2
1
0
4 3 2 2
1
0
2 2 2
1
0
2 2 2
1
0
&

,
_

1
1
]
1

+
+
+

A
A
A
dx x x x A
dx x x x A
dx x x A
dx
( )
( ) ( )
( )
( )
2
1
8
%
1
:
1 2
4
1
30 8
2 30 8
1 30 8
8
8 8
% : 4
1
0
: 4 3
1
0
2 2
1
0
&
1
0
&
> <
1
1
]
1

+ > <
+ > <
> <
> <
> <

x
x
dx x x x x
dx x x x x
dx x x
dx x x
Expectation Values
4
CHEM 342. Spring 2002. Problem Set #2. Answers.
=. 6or the wave !n"tion

## an# the operator 8 0 give an e9pression that "o!l# be !se# to

"al"!late the average val!e obtaine# rom repeate# meas!rements ,i.e. show an e9pression or
> <
8
..
( )

> <
d
d
&
&
8
8
or
( ) > <

d 8 8
&
0 where

is normali4e#.
Particle In a Box
>. Cal"!late the val!e o A so that
a
x n
A
n

sin
is normali4e# in the region a x 0 .
Hint\$
( ) ( ) C bx
b
x
dx bx +
,
_

2 sin
4
1
2
sin
2
( ) ( )
1
2
1 0 sin 2 sin
4 2
1
2
sin
4 2
1 sin
1 sin
1
2
2
0
2
0
2 2
0
2
0
&

,
_

1
]
1

1
]
1

,
_

1
]
1

a
A
n
n
a a
A
a
x n
n
a x
A
dx
a
x n
A
dx
a
x n
A
dx
a
a
a
a
n n
3hereore0
a
A
2

Note\$
( ) 0 2 sin n
or n - integer.
10. 6or a parti"le in a one<#imensional bo9
( ) a x 0
0 we !se# eigen!n"tions o the
orm
( ) kx Asin
. E9plain wh2 we "o!l# not !se
,a.
kx
Ae
,b.
( ) kx A"os
,a. 3he wave !n"tion m!st be 4ero or x - a. / k is a real n!mber0 then
kx
e "annot it
this bo!n#ar2 "on#ition.
,b. 3he bo!n#ar2 "on#itions also re1!ire that
0
when x - 0. 3his "annot be tr!e or
the "osine !n"tion be"a!se "os 0 - 1. 3hereore0 the allowe# eigen!n"tion m!st be
o the orm
( ) kx Asin
.
:
CHEM 342. Spring 2002. Problem Set #2. Answers.
11. 3he gro!n#<state wave !n"tion or a parti"le "onine# to a one<#imensional bo9 o
length L is
,
_

,
_

L
x
L
sin
2
2 7 1
. 3he bo9 is 10.0 nm long. Cal"!late the probabilit2 that the
parti"le is between 4.>: nm an# :.0: nm. Hint\$
( ) ( ) C bx
b
x
dx bx +
,
_

2 sin
4
1
2
sin
2
( ) ( )
020 . 0
0 . 10
>: . 4 2
sin
0 . 10
0: . : 2
sin
2
1
0 . 10
>: . 4 0: . :
2
sin
2
1
2
sin
4 2
2
sin
2
sin
2
0: . :
>: . 4
0: . :
>: . 4
0: . :
>: . 4
2
0: . :
>: . 4
2
0: . :
>: . 4
&

1
]
1

1
]
1

,
_

1
]
1

,
_

,
_

1
]
1

,
_

,
_

1
]
1

,
_

,
_

P
P
L
x
L
x
P
L
x L x
L
P
dx
L
x
L
P
dx
L
x
L
P
dx P
12. *hat is the gro!n# state energ2 ,i.e. n - 1. or an ele"tron that is "onine# to a bo9
whi"h is 0.2 nm wi#e. ?Hint\$ Plan")@s "onstant0 h,is
34
10 %2% . %

A s5 the mass o an ele"tron0
me0 is
31
10 10> . >

)gB
( ) ( )
( )( )
A 10 :0% . 1
m 10 2 . 0 )g 10 10> . > =
1 s A 10 %2% . %
=
1=
2
> 31
2
2
34
2
2 2

E
E
ma
n h
E
Uncertainty
13. 3he spee# o a "ertain proton is 4.: 10
:
m7s along the x<a9is. / the !n"ertaint2 in its
moment!m along the x<a9is is 0.010 C0 what is the ma9im!m !n"ertaint2 in its lo"ation along
the x<a9is ,i.e. x .+
( )
( ) v 00010 . 0
C 010 . 0
0
m p
p p
x
x

%
CHEM 342. Spring 2002. Problem Set #2. Answers.
( )
( )
( ) ( )( )
m 10 01 . ;
s m 10 : . 4 )g 10 %;3 . 1 00010 . 0 4
s A 10 %2% . %
v 00010 . 0 4
4
4
10
1 : 2;
34

x
x
m
h
x
p
h
x
h
p x
x
x
Tunneling
14. 3he wave !n"tion insi#e an ininitel2 long barrier o height V is
kx
Ae

.
Cal"!late ,a. the probabilit2 that the parti"le is insi#e the barrier5 an# ,b. the average penetration
#epth o the parti"le into the barrier ,i.e. the e9pe"tation val!e > < x .. De"a!se the barrier is
ininitel2 long0 this wave !n"tion is vali# or < < x 0 . Hint\$
+

1
E
n
ax n
a
n
dx e x

2
2
0
2 2
0
&
2
2
0
2
2
0
2 2
0
&
4
2 2
1
0
2
k
A
dx e xA dx x x
k
A
k
A
k
e
A dx e A dx P
kx
kx
kx
> <

1
]
1

1
]
1