Particle in a Box

This simple example of quantum behavior is also often referred to as the standing wave.
Although having no direct counterpart in the physical world the solutions are related to
real problems such as a violin string !or any stringed instrument" an electron in a
orbital !viewing only the location in one dimension along the bonding axis between the
two nuclei" and translational motion of gas particles when expanded to # dimensions.
The model$ %magine a particle in a box of length a. There is & chance of finding the
particle outside the box. 'ince
(
is the probability then must ) & outside the box and
also at each wall to satisfy the continuity requirement for *+ wave functions. ,e will
arbitrarily define the left wall at the box at position x ) & in our -. x direction. Thus at
the right wall x ) a. The potential energy is & everywhere in the box and at the walls
!otherwise the particle could escape". /ne of the things that can be 0nown about such a
particle is its energy !only because the model assumes 1 ) & and does not change with
time". This is found by solving the time2independent 'chr3dinger equation for the wave
function4
5 ) 6
5 = (27
2
/2m"
2
+ 1 = 7
2
/2m 8d
(
! "9dx
(
: ; &
7
2
/2m d
(
!"9dx
(
) 6
<earranging as a differential equation 4.
d
(
!"9dx
(
) !2(m697
2
)
Thus the function must be an eigen function of the (
nd
derivative operator. 'ome
functions that will satisfy this requirement are exp!cx" sin!cx" cos!cx" or sinc!cx" ;
cos!cx". 'electing the proper function is a trial and error process. ,ell begin with the
function sinc!cx" ; cos!cx" because it wor0s and illustrates some features of the process.
The constants A = B are added as normali>ation constants. These are required so that
(

must ) - when integrated over the entire dimensions of the box i.e. x ) & to a.
) A sin!cx" ; B cos!cx"
'ince ) & at x ) & and since the cos!&" is - then B must be equal to &. %n essence we
can drop the cosine term from the wave function.
) A sin!cx"
'ince ) & at x ) a and since this is only true if ca ) n where n ) any ; integer. !n
cannot equal & since would thus ) & and &
a

(
dx would also equal & in violation of the
normality requirement of the wave function." Thus c must ) n9a. n is referred to as the
quantum number. %t is the integral restriction on this number that quanti>es or restricts
the values of the wave function to certain states. 6ach state has its own wave function
designated n. Thus allowed states for the particle in a box include - ( # 4 etc. up
to n ) .
n ) A sin!nx9a"
?ow we can solve the @amiltonian to get 6. % will reinsert c and then change it to n9a at
the end to avoid excessive terms.
d
(
8Asin!cx":9dx
(
) A d
(
8sin!cx":9dx
(
-
st
derivative ) c cos!cx"
(
nd
derivative ) 2c
(
sin!cx"
2c
(
!Asin!cx"" ) !2(m697
2
) !Asin!cx""
2c
(
) !2(m697
2
)
En ) c
(
7
2
/(2m" ) n
2
h
2
/(8ma
2
)
The constant A placed before the sine function is there to guarantee that the function can
be normali>ed. This is one aspect of the requirement that is well2behaved such that the
probability is finite and &
a
AA
(
dx ) -. Thus it is called the normali>ation constant.
&
a

(
dx ) -
A
(
&
a
sin
(
cx dx ) -
sin
(
cx dx ) x9( B 8sin!(cx":9!Cc"
A
(
! a9( B & B & ; &" ) -
A
(
) (9a
A ) !(9a"
-9(
Thus we now 0now the following about the particle in a one dimensional box4
n = (2/a)
1/2
sin(nx/a)
En = n
2
h
2
/(8ma
2
)
Dan we calculate the exact position or momentum of the particle in the boxE ?oF
Because of the @eisenberg Gncertainty Principle which also manifests itself in the fact
the is not an eigen function of either the position operator !x" or the momentum
operator !79i d! "9dx
(
. @owever we can calculate the average position !which should
obviously be a9( or the center of the box" and the average momentum !which should
obviously be & since the particle will spend an equal time traveling in opposite
directions".
<x> = 0
a
x dx = a/2
<px> = /i 0
a
d()/dx dx = 0
Thus for the particle in a box we can
calculate the energy average position and
average momentum for each state. But we
can never 0now either the exact position or
the exact momentum !without opening the
box and measuring the particle and thus
changing9stopping its motion".
The figure at the right plots n for the first
four states. ?ote the probability is found by
ta0ing n
(
and will always be positive. ?ote the graphical analogy to a stringed
instrument.
Particle in a #. Box
m ) mass ab = c ) length of box in x y = > dimensions
application$ translational energy of ideal gas atom9molecule.
-. !xy>" ) H!x" I!y" J!>" = 5 ) 27
(
9(m !d
(
9dx
(
; d
(
9dy
(
; d
(
9d>
(
" ) 6
This is presently an assumption 2 that !xy>" can be represented !by a process called
separation of variables" by a product of functions each of which is dependent on a
single positional variable only. %t can be proven that if such a well behaved solution to the
@amiltonian 6quation listed above exists then can be represented in the form HIJ.
(. d
(
9dx
(
) H!x"I!y"J!>" etc.......
5 ) 6 ) 2 7
(
9(m 8H!x"I!y"J!>" ; H !x"I !y"J!>" ; H !x"I!y"J!>":
#. 6 ) 2 7
(
9(m 8H!x"I!y"J!>" ; H !x"I !y"J!>" ; H !x"I!y"J!>":
22222 222222222222222222222222222222222222222222222222222222222222222222
!xy>" H!x" I!y" J!>"
= 6 ) 2 7
(
9(m H!x"9H!x" 2 7
(
9(m I !y"9I!y" 2 7
(
9(m J!>"9J!>" ) 6x ; 6y ; 6>
C. %f we use the -. particle in a box solution for !x" as H!x" then 6x is a constant that is
independent of x !and y or >". <epeating the same process for I = J gives ........
K. H!x" ) !(9a"
-9(
sin!nxx9a" $ I!y" ) !(9b"
-9(
sin!nyy9b" $ J!>" ) !(9c"
-9(
sin!n>>9c"
!xy>" ) !(9a"
-9(
sin!nxx9a" !(9b"
-9(
sin!nyy9b" !(9c"
-9(
sin!n>>9c"
) !L9abc"
-9(
sin!nxx9a" sin!nyy9b" sin!n>>9c"
6 ) 6x ; 6y ; 6> ) !nx
(
h
(
9Lma
(
" ; !ny
(
h
(
9Lmb
(
" ; !n>
(
h
(
9Lmc
(
"
) h
(
9Lm !nx
(
9a
(
; ny
(
9b
(
; n>
(
9c
(
"
if the box is a perfect cube such that a ) b ) c then ....... 6 ) h
(
9Lm 8!nx
(
; ny
(
; n>
(
"9a
(
:
?otice that symmetry causes degeneracy. Because the dimensions of the box are the same
in different directions !symmetry" there are multiple states with identical energies
!degeneracy".