Lecture 10: Particle in a Box-II.

Lecture on-line
Particle in a box-II (PowerPoint)
Particle in a box-II (PDF format)
Assigned problems
Handout for lecture
Writeup on particle in a 3D-box
Translational Motion
12.1 A Particle in a Box
(d) The properties of the solution
12.2 Motions in two dimensions
Tutorials on-line

Basic concepts
Observables are Operators - Postulates of Quantum
Mechanics
Expectation Values - More Postulates
Forming Operators
Hermitian Operators
Dirac Notation
Use of Matricies
Basic math background
Differential Equations
Operator Algebra
Eigenvalue Equations
Extensive account of Operators
Audio-visuals on-line
Particle in a box (PowerPoint)
(good short account of particle in a box by the Wilson
group, ****)
Particle in a box (PDF)
(good short account of particle in a box by the Wilson group,
****)
Slides from the text book (From the CD included in Atkins ,**)
X=0
V=
X=l
V=
V= 0
V V
Region I Region II Region III

For regions I and III
-
2m
x)
x) =E x)
-
2m
x)
x) =E x)

x) =
1
2m
x)
h
h
h
2 2
2
2 2
2
2 2
2
d
dx
V
d
dx
d
dx

(
( (
(
( (
(
(
+
+

:
-
2m
x)
x) =E x)
-
2m
x)
=E x)

For region II
V
h
h
2 2
2
2 2
2
d
dx
d
dx

(
( (
(
(
+
Review particle in1- D box.
Schrdinger eq.
The particle in a box...
one dimension
E
h n
ml

2 2
2
8
Review particle in1- D box.
Energy and wavefunction
Wavefunctions
n
x =
2
l l
n = 1, 2, 3, 4....
n

sin[ ]
The particle in a 1D box...propeties of the solutions
Possible expectation values < A >

A
i
d
dx

h
Momentum


Expectation value of p
p p dx
i l
np
l
x
d
dx
np
l
x dx
i l
np
l
x
np
l
np
l
x dx
x
x n x n
l
l

<

sin[ ]
sin[ ]
sin[ ]( ) cos[ ]
* *
>

h
h
2
2
0
0
=
2
l l
n = 1, 2, 3, 4....
n

sin[ ]
n
x

< >

sin cos sin p
i
d
i
d
x
n n
=
h h 2
l
1
l


0 0
2 0
Introducing x dx n =
n
l
; d
n
l
limits : to

; 0


h h h
i l i l
n
i l
n
1
2
2
1
2
0 2
1
2
1 1 0
0
[cos ] [cos cos ] [ ]

Expectation value < p

for particle in 1- D box
x
>
=
2
l l
= - i
2
l
exp
l
+i
2
l
exp
l
which is a superposition of eigenfunctions to p with
eigenvalues
2l
and -
2l

n
x

sin[ ] [ ] [ ]

n
x i
n
x i
n
x
nh nh

< >

P
x
= 0
Expectation value < p
for particle in 1- D box
x
>
The particle in a 1D box...
propeties of the solutions
Does the particle move ? What would be the outcome
of a meassurement of P
x
?
The particle in a 1D box...
propeties of the solutions
Possible expectation values < A >

A
m
d
dx
= - Kinetic energy
h
2 2
2
2

Does the particle move ? What would be the outcome
of a meassurement of P
x
2
?
=
2
l l
n = 1, 2, 3, 4....
n

sin[ ]
n
x
Expectation value < p
for particle in 1- D box
x
2
>

Expectation value of p
p
l l l
l l l
x
2
x
2

( sin[ ]) ( )( cos[ ])
( )( )( )( sin[ ])

n
n
d
dx
l
n
x
d
dx
n
l
n
x
n n
l
n
x
h n
l


h h
h
2
2
2
2
2
2 2
2
2 2
1
2
4
Expectation value of p
p p p
x
2
x
2
x
2
x
2

* *
< >




n n n n
dx
h n
l
dx
h n
l
2 2
2
2 2
2
4 4
The particle in a 1D box...propeties of the solutions
Wavefunctions
n
x =
2
l l
n = 1, 2, 3, , 4, 5, 6...
n

sin[ ]
We x
Thus
observe that has n- 1 nodes where
(green) has zero; (blue) has one; (cyan) has one
etc..
n n


( ) . 0
1 2 3
We
l x l x x
o o o
also observe that for n odd are symmetrical around midpoint at x = l/2
where x is any value o < l/2
We call such functions even
n
n n o

( / ) ( / ) 2 2 + >
We
l x l x x
o o o
also observe that for n even are asymmetrical around midpoint at x = l/2
where x is any value o < l/2
We call such functions odd
n
n n o

( / ) ( / ) 2 2 + >
The first five normalized wavefunctions
of a particle in a box. Each
wavefunction is a standing wave, and
successive functions possess one
more half wave and a correspondingly
shorter wavelength.
Properties of : Nodes
and parity
n

Why do different solutions and have

different number of nodes if n m ?
n

m

Because must have both positive an negative

regions for to integrate to zero
n m
-
m


n
dx

Two functions are orthogonal if the integral of their

product is zero. Here the calculation of the integral
is illustrated graphically for two wavefunctions of a
particle in a square well. The integral is equal to the
total area beneath the graph of the product, and is
zero.
The particle in a 1D box...propeties of the solutions
Properties of :
Origin of Nodes
n

Particle in 2D box

Particle at : r = xe ye
x y
v
r r
+
Total E
pot
Energy of particle E = E
kin
+
E
m
p p V x y H
x y
+ +
1
2
2 2
[ } ( , )

Transition to QM
p
i
d
dx
p
i
d
dy
H
m
d
dx
d
dy
V x y
x y

;
[ ] ( , )

+ +
h h
h
2 2
2
2
2
2
Hamiltonian and
Schrdinger eq. in 2D

We have for the Schrdinger eq
m
d
dx
d
dy
V x y E
.
h
2 2
2
2
2
2
[ ] ( , )

+ +
Particle in 2D box
We must solve H = E
We assmume :

V = 0
0 a
x
y
V =
V =
V =
V =
Thus (x, y) = 0 outside box.

Inside box we must solve

h
2 2
2
2
2
2
0
m
d
dx
d
dy
V x y E
with V x y
[ ] ( , )
( , )

+ +

Boundary conditions
Separation of variables
We shall look for solutions of the form
is a product of two functions depending
on a single variable (separation of variables)

( , ) ( ) ( )
( , )
x y f x f y
where x y

1 1

For this to be a solution we must have
h
2 2
2
2
2
2m
d
dx
d
dy
V x y E [ ] ( , )

+ +

or
m
d f f
dx
d f f
dy
V x y f f E f f
h
2 2
12
2
2
12
2
12 12
2
[
( ) ( )
] ( , )( ) ( ) + +
Particle in 2D box

or
m
f x f y f x f y Ef x f y
h
2
1 2
1
2
1
2
2
[ ( ) ( ) ( ) ( )] ( ) ( )
" "
+

or
m
f x
f x
f y
f y
E
h
2
1
1
2
2
2
[
( )
( )
( )
( )
]
" "
+
Particle in 2D box

For a given x this relation
must hold for all x Thus
m
f x
f x
E
also
m
f y
f y
E
E E
x
y
x y

. :
E=


+
h
h
2
1
1
2
2
2
2
2
"
"
( )
( )
( )
( )
]

h
2
1
1
2
2
2m
f x
f x
f y
f y
E [
( )
( )
( )
( )
]
" "
+
Separation of variables
V = 0
0 a
x
y
V =
V =
V =
V =

We have
m
f x
f x
E
f f a
m
f x E f x
f x
a
n
a
x
h n
ma
x
x
x x

; o x a
= 0

E

x

h
h
2
1
1
1 1
2
1
1
1
2 2
2
2
0
2
2
8
"
"
( )
( )
( ) ( )
( ) ( )
( ) sin[ ];

Separation of variables
Particle in 2D box
V = 0
0 a
x
y
V =
V =
V =
V =
Separation of variables
Particle in 2D box

We have
m
f y
f x
E
f f b
m
f y E f y
f y
b
n
b
x
h n
mb
y
y
y y

; o y b
= 0

E

y

h
h
2
2
1
2 2
2
2
2
2
2 2
2
2
0
2
2
8
"
"
( )
( )
( ) ( )
( ) ( )
( ) sin[ ];

V = 0
0 a
x
y
V =
V =
V =
V =
Particle in 2D box
Thus
Thus (x, y) =
4
ab

sin[ ] sin[ ]
n
a
x
n
b
y
E
h n
ma
h n
mb
x
y
x
y
+
2 2
2
2 2
2
8 8
For a = b
E
h
ma
n n
x y
+
2
2
2 2
8
[ ]
Dege
nerate

Dege
nerate

For a = b
(x, y) =
2
a

sin[ ] sin[ ]
[ ]
n
a
x
n
a
y
E
h
ma
n n
x
y
x y
+
2
2
2 2
8
n n E( )

x x
h
ma
2
2
8
1 1 2

2 1 5
1 2 5
2 2 8
2 3 13
3 2 13

Separation of variables
What you should learn from this lecture
1
1 2 3
.
( , , ...)
.
The solutions to the Schrdinger eq. for a 1D
particle in a box are not eigenfunctions
to p They represents states for which a measurement
of p would give
hn
2l
and < p = 0
n
x
x x
n
>
2
1 2 3
4
4
2
2
2
2
.
( , , ...)
.
The solutions to the Schrdinger eq. for a 1D
particle in a box are eigenfunctions
to p with eigenvalues
h
They represents states
fo r which a measurement of p would give
h
n
x
2
2
x
2
2
n
n
l
n
l

3
1 2 3
.
( , , ...)
*
The solutions to the Schrdinger eq. for a 1D
particle in a box have nodes to
satisfy the orthonormality condition
n

n
dx
m n nm

What you should learn from this lecture
4.
(x, y) =
4
ab

For a 2D box of sides a and b the wavefunction
is zero outside the box and given by
inside

( , )
sin[ ] sin[ ] ,
n
x
n
y
x
y
y
x
y
n
a
x
n
b
y n
E
h n
ma
h n
mb
(n positive integers)
The corresponding energy is given by
x
+
2 2
2
2 2
2
8 8
V = 0
0 a
x
y
V =
V =
V =
V =
The particle in a 1D box..Appendix on orthonormalization
the two solutions and have
the properties that
if m n
We say that and are
orthogonal
n m
n
m
-
n m



*

dx 0
We have

=
2
l l
u = m,n
2
l l
2
l l

n
m
-
u
-
I dx
with
u
I
n
x
m
x dx
ce
nm
nm

*
sin[ ]
sin[ ] sin[ ]
sin sin sin [cos( ) cos( )]
1
2
Thus
1
l l
1
l l
l
l
l
l
-
I
n m x
dx
n m x
dx
or
I
n m x
n m
n m x
n m
I n m
n m
nm
nm
o
l
nm

+
+
,

,
,
,
]
]
]
]
]
+
+

cos[
( )
] cos[
( )
]
sin[
( )
( )
sin[
( )
( )
{ sin[( ) ]
sin[( ) }

0 0
0
We thus have
if n m
if n m

n
m
-
n
m
-
n
m
-



*
*
*

dx
dx
or
dx
nm
0
1
The particle in a 1D box...
conjugated molecules
A An n a a c ct t u ua al l s sy ys st t e em m t t h ha at t a ap pp pr r o ox xi i m ma at t e es s t t h he e p pa a r rt t i i c cl l e e s s- - i i n n- - a a- -
b bo ox x p pr r o ob bl l e em ms s: :
A number of molecules have conjugated -bonds in which the
electrons are delocalized over the whole molecules
H H H H H H
H
2
C=C C=C--C=C- C=CH
2
(1) They consists in the first place of a chain of atoms held
together by a system of -bonds
(2) In addition to the electrons that participate in the -bonds there
are present in the molecule electrons that are delocalized.These
electrons are refered to as -electrons.We shal refer to their
number as n

Appendix for Lab 5 on Dyes

For the particle in a box we have the energy levels

E
E
E
E
n
n-1
2
1
With the energies
E
n
=
h
2
n
2
8ml
2
and associated orbitals

n
(x) =
(
,
j
,
(
\
2
l
sin
nx
l
The particle in a 1D box...
conjugated molecules
Appendix for Lab 5 on Dyes
To obtain the many-electron system of lowest energy we begin to
fill the levels of lowest energy

E
E
E
E
n
n-1
2
1
For n

-electrons,where we shal assume that n

is even, a total
of
n

2
levels will be occupied
The particle in a 1D box...
conjugated molecules
Appendix for Lab 5 on Dyes
E
E
2
1
E
n

2
E
n

2
+1
HOMO
LUMO
The total energy of the system is given by
E
ground
= 2*E
1
+ 2*E
2
+ ........ 2*E
n
2
The particle in a 1D box...
conjugated molecules
Appendix for Lab 5 on Dyes
For the first excited state we promote one electron out of the
HOMO and into the LUMO
E = E
LUMO
- E
HOMO
=
h
2
(
,
,
j
,
(
(
\
n

2
+ 1
2
8ml
2
-
h
2
(
,
,
j
,
(
(
\
n

2
2
8ml
2
E =
h
2
8ml
2
(n

+1)
This is the energy required to excite the groundstate to the first
excited state.We have that the excitation energy E is related to
the frequency at which the excitation occure by
=
1
hc
E
Thus the absorption energy frequency is
=
h
8ml
2
c
(n

+1)
The particle in a 1D box...
conjugated molecules
Appendix for Lab 5 on Dyes
Particle in 2D box

For a = b
Thus (x, y) =
2
a
fold generate

sin[ ] sin[ ]
[ ]
n
a
x
n
a
y
E
ma
n n
ma
n n
One
x
y
x y
x y
+

h h
2
2
2 2
2
2
8
2
8
1
The wavefunctions for a particle
confined to a rectangular surface
depicted as contours
of equal amplitude.
(a) n
1
= 1, n
2
= 1, the state of
lowest energy
Appendix : Solutions to
particle in 2D- box
Particle in 2D box
Degenerate : States with the same
energy have different wavefunctions
For a = b
Thus (x, y) =
2
a
; n
fold generate

sin[ ] sin[ ]
[ ]
n
a
x
n
a
y
E
h
ma
n n
h
ma
n n n
two
E
h
ma
x
y
x y
x y x y
+

2
2
2 2
2
2
2
2
8
2
8
1 2 2 1
5
8
The wavefunctions for
a particle confined to a
rectangular surface
depicted as contours
of equal amplitude.
(b) n
1
= 1, n
2
= 2,
(c) n
1
= 2, n
2
= 1,
Particle in 2D box
The wavefunctions for a particle confined to a
square surface. Note that one wavefunction can be
converted into the other by a rotation of the box by
90. The two functions correspond to the same
energy. Degeneracy and symmetry are closely
related.
Appendix : Solutions to
particle in 2D- box
Particle in 2D box
For a = b
Thus (x, y) =
2
a

sin[ ] sin[ ]
[ ]
n
a
x
n
a
y
E
h
ma
n n
h
ma
x
y
x y
+
2
2
2 2
2
2
8
2
8
n n
one
E
h
ma
x y

2 2
8
8
2
2

fold generate

Appendix : Solutions to
particle in 2D- box
Particle in 2D box
For a = b
Thus (x, y) =
2
a
; n
fold generate

sin[ ] sin[ ]
[ ]
n
a
x
n
a
y
E
h
ma
n n
h
ma
n n n
two
E
h
ma
x
y
x y
x y x y
+

2
2
2 2
2
2
2
2
8
2
8
3 2 2 3
13
8
Appendix : Solutions to
particle in 2D- box