Lecture 9: Particle in a Box-I. The material in this lecture covers the following in Atkins. Translational Motion 12.

1 A particle in a box (a) The Schrdinger Equation (b) The acceptable solution (c) Normalization (d) The properties of the solutions Lecture on-line Particle in a box-I (PowerPoint) Particle in a box-I (PDF format) Handout for lecture (PDF) Writeup on solving differential equations (PDF) Writeup on particle in 1-D box (PDF)

Tutorials on-line
Basic concepts of importance for the understanding of the postulates 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 ,**)

The particle in a box...one dimension For a particle moving in one dimension we have for the Hamiltonian : x h2 d2 p2 + V(x) H= + V(x) = 2 2m 2m dx
the particle is described by the wavefunction ( x) which is a solution to the S.W.E
H ( x) = E ( x) h 2 d2 ( x) + V( x ) ( x) = E ( x) 2 2m dx where E is the energy of the particle

The particle in a box...one dimension

h2 d 2 ( x) + V ( x ) ( x) = E ( x) 2 2m dx

We shall consider a case in which V(x) is given by :

V V= X=0 V= 0 X=l V V=

Thus inside" the box" between x = 0 and x = l we have V = 0

Outside the " box" V =

The particle in a box...one dimension V V

V= X=0
We have :

V= 0 X=l

V=

h 2 d 2 ( x) I: + ( x) = E ( x) X < 0 2 2m dx

h2 d 2 ( x) + V ( x) = E ( x) II : 2 2m dx

0< X <l

h2 d 2 ( x) + ( x) = E ( x) X > l III : 2 2m dx

The particle in a box...one dimension

For region I : h2 d 2 ( x) + ( x) = E ( x) X < 0 2 2m dx

Or : h 2 d 2 ( x) = [E ] ( x) 2 2m dx Since E << (Physical Argument)

h 2 d 2 ( x) = ( x) 2 2m dx

V V= X=0 V= 0

V V= X=l

Thus 1 h 2 d 2 ( x) = ( x) 2 2m dx

The particle in a box...one dimension

We have 1 h2 d 2 ( x) ( x) = 2m dx 2 <T > = h2 2m *

V V= 0 V= X=l

Must be finite
d 2 dx 2 dx

V= X=0

hus : ( x) = 0 for x < 0

Also for region III where X > l 1 h2 d 2 ( x) we have ( x) = 2m dx 2

and must require ( x) = o for x > l

The particle in a box...one dimension

Region I

Region II

Region III

V= X=0

V= 0 X=l

V=

We have I ( x) = III ( x) = 0
Thus PI ( x ) = I * ( x)I ( x) = 0
{ Probability of finding particel in I PIII ( x ) = III * ( x)III ( x) = 0 { Probability of finding particel in III

"No particle outside box"

The particle in a box...one dimension

Region I

Region II

Region III

V=

V= 0

V=

X=0 X=l Now for region II :

h 2 d2 ( x) + V ( x) = E ( x) 2 2m dx h 2 d2 ( x) = E ( x) 2 2m dx

d 2 ( x) 2mE 2 = 2 ( x) dx h or d 2 ( x) 2mE 2 2 = - k ( x) ; k = 2 2 dx h

The particle in a box...one dimension

d 2 ( x)

dx 2 We have

2 ( x) ; k 2 = 2mE = -k h2

d 2cos[kx] dx 2 and d 2sin[kx] dx 2

= k 2cos[kx]

= k 2sin[kx]

Thus ( x ) = A cos[kx ] + B sin[kx ]

The particle in a box...one dimension Thus (x) = A cos[kx] + B sin[kx]

V = 0 X=0 ()=0

V = 0 X=l (l)=0

We must have II (x) = 0 since the wavefunction must be continous according to Born Thus we get the BOUNDARY condition : II ( 0 ) = A cos[k0] + B sin[k0] = 0

which is only possible if A = 0 Thus : ( x ) = B sin[kx]

The particle in a box...one dimension Thu s (x) = B sin[kx] We must also have (l ) = B sin[kl ] = 0 V V possible solutions : = 0 = 0
X=0 ()=0
B=0

X=l (l)=0
or k = 0

Both trivial and will make the wave function zero everywhere

Not acceptable on physical grounds

The particle in a box...one dimension

Thus (x) = B sin[kx ] V = 0 X=0 ()=0 V = 0 X=l (l)=0

k' Non trivial solution Introducing k = l k' For x = l : II ( l ) = B sin[kl] = B sin[ l] = B sin[k' ] l

For x = l II ( l ) = B sin[k' ] = 0

for k' = n

n = 1, 2, 3,.....

The particle in a box...one dimension

n We have the non - trivial solution : ( x ) = B sin[ x] l n = 1; 2; 3,....
n n We have further that sin[ x] = sin[ x] l l Thus we need only consider solutions n = 1,2,3,...

Further since d 2 ( x) 2mE h2k 2 ; E= = - k 2 ( x) ; k 2 = 2m dx 2 h2

n k= ; n = 1,2,3,4. l

E=

h2 n 2 2 8ml 2

h2n2 8ml 2

Note E 0

The particle in a box...one dimension

E=

h2n2 8ml 2

The allowed energy levels for a particle in a box. Note that the energy levels increase as n2, and that their separation increases as the quantum number increases.

Lowest level n = 1, energy not zero why ?

The particle in a 1D box...propeties of the solutions

Wavefunctions n n = 1, 2

2 n = sin[ x ] l l

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.

The particle in a 1D box...propeties of the solutions

Wavefunctions n n = 1, 2
From normalization

2 n = sin[ x ] l l

Pr obability : *n n n = 1, 2 Note particle most likely to be found in middle for n = 1

Energy :
(a) The first two wavefunctions, (b) the corresponding probability distributions, and (c) a representation of the probability distribution in terms of the darkness of shading.

E=

h2n2 8ml 2

n = 1,2,..

The particle in a 1D box...propeties of the solutions

For n n = 1
probability *n n dx of finding particle largest in middle of box

For n n = large (20)

probability *n n dx of finding particle same throughout box (classical limit)

What you should learn from this lecture 1. For the particel in a box You should remember the dependence of the energy on the quantum number n and the box length l. You should also note the lower limit (n = 1) for n and the consequence it has for the minimum energy (zero point energy)

Energy : E= h2n2 8ml 2 n = 1,2,..

What you should learn from this lecture

2. You should also know roughly the form of the statefunctions n . Especially, you should note that n nodes.
2 n Wavefunctions n = sin[ x] n = 1,2 l l

The particle in a box...one dimension Appendix : Normalization

For the solution (x) = B sin[
l * 0l *

n x] we can fix B by the normalization requiremet l

ll * l

* ( x ) ( x )dx = I ( x ) I ( x )dx + II ( x ) II ( x )dx + III ( x ) III ( x )dx 0

n 2 n l Thus : I = sin[ x ] dx = 1 2 sin2d I= B l 0 0 n Introducing : n l 1 1 n n sin 2 I = B2 = x d = dx n 2 4 o l l n 2 l 2 l Limits of : [o o + 0] I = B I=B 2 2 n x = 0 = 0: x = l = n

l
Thus B2 = 2 2 and B = exp[i] l l 2 2 2 where is any real number. Note : B2 = B*B = exp[ i] exp[i] B2 = l l l and | B | = 2 l

Thus

The particle in a box...one dimension

2 n sin[ ] exp[i] l l

( x , t ) = f ( t ) ( x )
2 n i sin[ ] exp[i Et ] l l h

Appendix : Time Dependence

n (x) =

i Et f( t) = Exp h
Phase factor

n ( x, t) =

We shall deal (mostly) with time time independent (stationary) states where the properties are determined by time independent operators A where :
< A >= *n ( x, t)A *n ( x, t)dx = n i 2 sin[ ] exp[i Et]dx l l h 2 n i sin[ ] exp[ i + Et ]A l l h

The particle in a box...one dimension

< A >= *n ( x, t)A *n ( x, t)dx =

Appendix : Time Dependence

2 n i sin[ ] exp[ i + Et ]A l h l

2 n i sin[ ] exp[i Et]dx l l h sin ce A time - independent i i < A >= exp[ i + Et] exp[i Et] h h
2 n sin[ ]dx l l Thus n 2 n 2 < A >= sin[ ]]A sin[ ]dx l l l l

2 n sin[ ]]A l l

= *nA ndx we need only be concerned with the real solutions n = sin[ n ] l