Lecture 08: Schrödinger’s

Equation
and the Particle in 1D Box
(x)

U= U=
n=1 n=3

0 L x
n=2
 Content

Particle in a “Box” -- matter waves in an infinite
square well
 Wavefunction normalization
Last lecture: The time-independent SEQ (in 1D)
 2 d 2  ( x)
  U ( x ) ( x )  E  ( x )
KE term 2 m dx 2
Total E term
PE term
 Notice that if U(x) = constant, this equation has the simple form:
d 2
2
 C (x)
dx
2m
where C  2 ( U  E ) is a constant that might be positive or negative.


For positive C, what is the form of the solution?

a) sin kx b) cos kx c) eax d) e-ax

For negative C, what is the form of the solution?

a) sin kx b) cos kx c) eax d) e-ax
Last lecture: The time-independent SEQ (in 1D)
 2 d 2  ( x)
  U ( x ) ( x )  E  ( x )
KE term 2 m dx 2
Total E term
PE term
 Notice that if U(x) = constant, this equation has the simple form:
d 2
2
 C (x)
dx
2m
where C  2 ( U  E ) is a constant that might be positive or negative.


For positive C, what is the form of the solution?

a) sin kx b) cos kx c) eax d) e-ax

For negative C, what is the form of the solution?

a) sin kx b) cos kx c) eax d) e-ax
 Constraints on the form of (x)
 (x) corresponds to a physically meaningful quantity – the
probability of finding the particle near x. Therefore, in a region of
finite potential:

(x) must be finite, continuous and single-valued.

(because probability must be well defined everywhere)

d/dx must be finite, continuous and single valued.

(because d/dx is related to the classical momentum)

There is usually no significance to the sign of (x).

(it goes away when we take the absolute square)
{In fact, we will see that (x) can even be complex!}
 Exercise 1
1. Which of the following hypothetical wavefunctions for a
particle in some realistic potential U(x) is acceptable?
x x x
(a) (b) (c)

x x x

2. Which of the following wavefunctions corresponds to a

particle more likely to be found on the left side?
(a) (b) (c)
(x) (x) (x)

0 x 0 x 0 x
 Solution
1. Which of the following hypothetical wavefunctions for a
particle in some realistic potential U(x) is acceptable?

(a) x x x

(b) (c)

x x x

(a) Not acceptable (b) Acceptable (c) Not acceptable

xis not Both xand ddx ddxis not

continuous at x=0. are continuous continuous at x=0
everywhere
d
not defined.
dx
 Solution
2. Which of the following wavefunctions corresponds to a
particle more likely to be found on the left side?
(a) (b) (c)
(x) (x) (x)

0 x 0 x 0 x

None of them!
(a) is clearly completely symmetric. 
(b) might seem to be “higher” on
the left than on the right, but it
is only the absolute square the 0 x
determines the probability.
 Application of SEQ: “Particle in a Box”
 Recall, from last lecture, the time-independent SEQ in one dimension:

 2 d 2  ( x)
  U ( x ) ( x )  E  ( x )
KE term 2 m dx 2
Total E term
PE term
 As a specific important example, consider a quantum particle confined
to a small region, 0 < x < L, by infinite potential walls. We call this a
“one-dimensional (1D) box”.

U(x) This is a basic problem in “Nano-science”. It’s a

  simplified (1D) model for an electron confined in a
quantum structure (e.g., “quantum dot”), which
scientists/engineers make, e.g., at the UIUC
Microelectronics Laboratory! (www.micro.uiuc.edu)

‘Quantum
0 L
U = 0 for 0 < x < L dots’
U =  everywhere else
(www.kfa-juelich.de/isi/) (newt.phys.unsw.edu.au)
 Waves: Boundary conditions
 Boundary condition: Constraints on a wave where the potential changes
 E = 0 at surface of a metal filmDisplacement = 0 for wave on string

E=0
 If both ends are constrained (e.g., for a cavity of length L), then only
certain wavelengths  are possible:
n 
1 2L
2 L n = 2L
n= 1, 2, 3 …
3 2L/3 ‘mode index’

4 L/2
L
Rope Demo
 Particle in a Box (1)
 Solving the SEQ for the particle-in-a-box:
(a basic boundary-value problem)
 There are 2 distinct regions, (I) outside, and (II) inside the well

Region I: When U = , what is x? U(x)

 
d 2  ( x) 2m
2
 2 ( E  U ) ( x )  0 I II I
dx 

0 L
U = 0 for 0 < x < L
U =  everywhere else
 Particle in a Box (1)
 Solving the SEQ for the particle-in-a-box:
(a basic boundary-value problem)
 There are 2 distinct regions, (I) outside, and (II) inside the well

Region I: When U = , what is x? U(x)

 
d 2  ( x) 2m
 2 ( E  U ) ( x )  0 I II
dx 2
 I
 
For U = , the SEQ can only be satisfied if:
0 L
x = 0 U = 0 for 0 < x < L
U =  everywhere else

(otherwise, the energy would have to be infinite, to cancel U.)

Note: The infinite well is an idealization. On the atomic scale there are no infinitely
high and sharp barriers. (x) and d(x)/dx go to zero continuously near a boundary.
 Particle in a Box (2) U(x)
 
Region II: When U = 0, what is x?
d 2  ( x) 2m II
 ( E  U ) ( x )  0
dx 2 2
d 2  ( x)  2 mE  0 L
  2  ( x )
dx 2    U = 0 for 0 < x < L
U =  everywhere else
 Particle in a Box (2) U(x)
 
Region II: When U = 0, what is x?
II
d 2  ( x) 2m
 ( E  U ) ( x )  0
dx 2 2 
d 2  ( x)  2 mE  0 L
  2  ( x )
dx 2   

The general solution to this is:

2
 ( x )  B1 sin k x  B 2 cos k x where, k 

Oscillatory solutions!

Plugging (x) into

 2k 2 h2 Consistent with DeBroglie’s
the SEQ, we find E  hypothesis:
the requirement: 2m 2 m 2 p = h/ = ħk and E = p2/2m

B1 and B2 are coefficients to be determined by the boundary conditions.

 Particle in a Box (3) U(x)
 
 Matching wavefunctions at the boundaries:

The wavefunction takes on the following form:

I II I

Region I:  I( x )  0  

0 L
Region II:  II ( x )  B 1 sin k x  B 2 cos k x

Key point: The total wavefunction (x) must be

continuous at all boundaries !
 Particle in a Box (3) U(x)
 
 Matching  at the first boundary (x = 0)

The wavefunction takes on the following form:

I II I

Region I:  I( x )  0  

0 L
Region II:  II ( x )  B 1 sin k x  B 2 cos k x

Key point: The total wavefunction (x) must be

continuous at all boundaries !

At x = 0:  I ( x  0 )   II ( x  0 )
0  B1 sin 0   B 2 cos 0 

0  B2 because cos(0) = 1 and sin(0) = 0

So this “boundary condition” requires that there be no cos(kx) term!

 Particle in a Box (4) U(x)
 
 Matching  at the second boundary (x = L)

I II I
At x = L:  I ( x  L )   II ( x  L )

0  B1 sin k L   

0 L
This constraint forces k to have special values !

n 2
kn  , n  1, 2, ... Using k  we find : n   2 L
L 
This is precisely the condition we found for confined waves, e.g., EM waves
in a laser cavity:
n = c/f)
4 L/2 For matter waves, the
3 2L/3 wavelength is related
to the particle energy:
2 L En = h2/2m2
1 2L Therefore
In a confining potential, Particle Energy is Quantized.

• The discrete En are known as “energy eigenvalues”:

electron
n En n n  2 L

4 L/2 h2 1.505 eV  nm 2
En  2

2 m n 2n
3 2L/3
2 h2
2 L E n  E1n with E1 
8mL2
1 2L E1
U= U=
(x) En
U= U=
n=1 n=3 n=3

n=2
n=1
0 L x
n=2 0 L x
Allowed wavefunctions have an integral # of half-wavelengths
that precisely “fit” in the well.
In a confining potential, Particle Energy is Quantized.

• The discrete En are known as “energy eigenvalues”:

electron
n nEn n n  2 L

4 L/2 16E1 h2 1.505 eV  nm 2

En  2

2 m n 2n
3 2L/3 9E1
2 h2
E n  E1n with E1 
2 L 4E1 8mL2
1 2L E1
U= U=
(x) En
U= U=
n=1 n=3 9E1 n=3

4E1
n=2
E1
0 L x n=1

n=2 0 L x
Allowed wavefunctions have an integral # of half-wavelengths
that precisely “fit” in the well.
 Particle-in-Box: Example
 Calculate ground state energy and the photon energy for a transition.
An electron is trapped in a “quantum wire” that is L = 4 nm long. Assuming
that the potential seen by the electron is approximately that of an infinite
square well, estimate the ground (lowest) state energy of the electron.

What photon energy is required to excite the trapped electron to the next
available energy level (i.e., n = 2)?
U=
En U=
n=3

n=2
n=1
0 L x
 Particle-in-Box: Example
 Calculate ground state energy and energy for a transition.
An electron is trapped in a “quantum wire” that is L = 4 nm long. Assuming
that the potential seen by the electron is approximately that of an infinite
square well, estimate the ground (lowest) state energy of the electron.

Allowed energies for electron in a 1D box:

h2 1.505 eV  nm 2  n  2 L/n
En  
2 m2n 2n
h2 1.505 eV  nm 2 E1 = ground state
2
En  E1n with E1   energy (n = 1)
8 mL2 4 L2
1.505 eV  nm 2
E1  2
 0.0235 eV
4( 4 nm )
What photon energy is required to excite the trapped electron to the next
available energy level (i.e., n = 2)?
U=
En U=
n=3

n=2
n=1
0 L x
 Particle-in-Box: Example
 Calculate ground state energy and energy for a transition.
An electron is trapped in a “quantum wire” that is L = 4 nm long. Assuming
that the potential seen by the electron is approximately that of an infinite
square well, estimate the ground (lowest) state energy of the electron.

Allowed energies for electron in a 1D box:

h2 1.505 eV  nm 2  n  2 L/n
En  2

2 mn 2n
2 h2 1.505 eV  nm 2 E1 = ground state
En  E1n with E1  
8 mL2 4 L2 energy (n = 1)

1.505 eV  nm 2
E1  2
 0.0235 eV
4( 4 nm )

What photon energy is required to excite the trapped electron to the next
available energy level (i.e., n = 2)?
U=
En U=
n=3 E n  n 2E1
2 2
 
 E  2  1 E1
n=2 So, energy difference  3E 1
n=1 between n = 2 and n = 1 = 0.071 eV
0 L x levels:
 exercise 2
1. An electron is in a quantum “dot”. If we decrease
the size of the dot, the ground state energy of U= U=
the electron will En
n=3
a) decrease
b) increase n=2
c) stay the same n=1

0 L x

2. If we decrease the size of the

dot, the difference between two
energy levels (e.g., between n = 2
and 3) will

a) decrease
b) increase
c) stay the same
 exercise 2
1. An electron is in a quantum “dot”. If we decrease
the size of the dot, the ground state energy of U= U=
the electron will En
n=3
a) decrease
b) increase n=2
c) stay the same n=1
2
h
E1  0 L x
8mL2

2. If we decrease the size of the

dot, the difference between two
energy levels (e.g., between n = 2
and 3) will

a) decrease ΔE ~ E1
b) increase E3 - E2 = (9 – 4)E1 = 5E1
c) stay the same Since E1 increases, so does ΔE
 M. Nayfeh (UIUC) : New photonic and electronic
material -- Discrete uniform Si nanoparticles
• Transition from bulk to molecule-like in Si
• A family of magic sizes of
hydrogenated Si nanoparticles
• No magic sizes > 20 atoms for non-
hydrogenated clusters
• Small clusters glow: color depends on
size (“quantum confinement”) 
• Used to create Si nanoparticle 1 nm 1.67 nm 2.15 nm 2.9 nm
Blue Green Yellow Red
microscopic laser:
 Probabilities
What we measure in an experiment is the probability density, |(x)|2.
 n  Wavefunction = 2  n  Probability per
 n ( x )  N sin  x Probability amplitude
2 2
 n ( x )  N sin  x unit length
 L   L  (in 1-dimension)

 
U= U=
n=1

0 L x 0 L x

 

n=2
0 L x 0 L x

 

0 L x n=3
0 L x
 Supplementary Problem 1
 Suppose a ball of mass 1 g trapped in our (1-d) box - 1 cm wide - has an
energy of 10-10 J. What is its “quantum number”, n?
(Hint: = 1 x 10-34 J•s)

Answer: 1025
 Supplementary Problem 1
 Suppose a ball of mass 1 g trapped in our (1-d) box - 1 cm wide - has an energy of 10 -10 J. What is
its “quantum number”, n?
(Hint: h= 6.626 x 10-34 J•s, p = h/ =  k )

2
p 2n h2 h2  n 
En   2
  
2m 2m  n 2m  2L 

28mE 2 8  10  3 kg  10  10 J 4 2
n  2 L   10 m
h 43.9  10 68 J 2 s 2

n ~ 1025 !

  k n   n   
2 2 2 2

 or use: E n      ħ = 1.0546 x 10-34 J•s

 2m 2m  L  

2  2 n n  n 
Note : k    therefore  (x) = Nsin(kx) =Nsin  x 
 2L L  L 
 Supplementary Problem 2
Consider a particle in the n = 2 state of a box.
(x)
a) Where is it most likely to be found?
b) Where is it least likely to be found? U= U=
c) What is the ratio of probabilities for the
particle to be near x = L/3 and x = L/4? n=2

0 L/4 L/3 L x
 Supplementary Problem 2
Consider a particle in the n = 2 state of a box.
(x)
a) Where is it most likely to be found?
b) Where is it least likely to be found? U= U=
c) What is the ratio of probabilities for the
particle to be near x = L/3 and x = L/4? n=2

0 L/4 L/3 L x
Solution:
a) x = L/4 and x = 3L/4. Maximum probability is at max .

b) x = 0, x = L/2, and x = L. Minimum probability is at the nodes.

c) (x) = Nsin(2x/L) The sine wave must have nodes at x = 0, x = L,

and, because n = 2, at x = L/2 as well.

Prob(L/3) / Prob(L/4) Prob(x)

= |(L/3)|2 / |(L/4)|2
= sin2(2/3) / sin2(/2)
= 0.8662 = 0.75
0 L x