Quantum Mechanics 1 SPH 313

2.3.1 APPLICATIONS OF SCHRODINGER'S WAVE EQUATION

It is usually a very difficult problem to solve Schrodinger’s wave equation. However, there are three
simple scenarios :1. the particle in a box, 2. the finite potential well, 3. barrier penetration and
tunneling, which are readily solvable. These examples turn out not only to be instructive, but also to
have tremendous application to the understanding of matter in general and semi-conductivity in
particular. It will be seen later that semi-conductivity is a purely quantum phenomenon. There is no
classical road towards an understanding of semi-conductivity. Classical physics alone would never
have led to the discovery of semi-conductivity. The most tremendous improvement in our quality of
life through technology of the last century was the result quantum mechanics - the highest level of
abstraction achieved during the last century.

We will now apply Schrodinger's wave equation in several examples using various potential functions,
Vx. These examples will demonstrate the techniques used in the solution of Schrodinger's
differential equation and the results of these examples will provide an indication of the electron
behavior under these various potentials. We will utilize the resulting concepts later in the discussion
of semiconductor properties.

2.3.1 Electron in Free Space

As a first example of applying the Schrodinger's wave equation, consider the motion of an electron in
free space. If there is no force acting on the particle, then the potential function V(x) will be constant
and we must have E > V(x). Assume, for simplicity, that the potential function V(x) = 0 for all x.
Then, the time-independent free particle Schrodinger wave equation can be written from Equation
(2.13)
2x  2mEVx(x)  0
(2.13)
2x2 2
as
2x  2mE(x)  0
(2.19)
2x2 2
The solution to this differential equation can be written in the form
ix 2mE
x  Ae
ix 2mE
  Be  (2.20)
Recall that the time-dependent portion of the solution is
i E t
t  e  (2.21)
Then the total solution for the wave function is given by
   
x, t  Ae
i x 2mE Et  i x 2mE Et
  Be  (2.22)
This wave function solution is a traveling wave, which means that a particle moving in free space is
represented by a traveling wave. The first term, with the coefficient A, is a wave traveling in the x
direction, while the second term, with the coefficient B, is a wave traveling in the x direction. The

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value of these coefficients will be determined from boundary conditions. We will again see the
traveling-wave solution for an electron in a crystal or semiconductor material.

Assume, for a moment, that we have a particle traveling in the x direction, which will he described
by the +x traveling wave. The coefficient B = 0. We can write the traveling-wave solution in the form
 
x, t  Aeikx  t (2.23)
Where k is a wave number and is given by
k  2 (2.24)

The parameter  is the wavelength and, comparing Equation (2 23) with Equation (2.22), the
wavelength is given by
 h (2.25)
2mE
From de Broglie's wave-particle duality principle the wavelength is also given by
 h
p
(2.26)
A free particle with a well-defined energy will also have a well-defined wavelength and momentum.
The probability density function is  (x, t) *(x, t) = AA*, which is a constant independent of
position. A free particle with a well-defined momentum can be found anywhere with equal probability.
This result is in agreement with the Heisenberg uncertainty principle in that a precise momentum
implies an undefined position. A localized free particle is defined by a wave packet, formed by a
superposition of wave functions with different momentum or k values. We will not consider the wave
packet here.

2.3.2 The Infinite Potential Well

The problem of a particle in the infinite potential well is a classic example of a bound particle. The
potential V(x) as a function of position for this problem is shown in Figure 2.5.

Figure 2.5 Potential function of the infinite potential well.

The particle is assumed to exist in region II so the particle is contained within a finite region of space.
The time-independent Schrodinger's wave equation is again given by Equation (2.13) as
2x  2mEVx(x)  0
(2.13)
2x2 2

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where E is the total energy of the particle. If E is finite, the wave function must be zero, or  (x) =
0, in both regions I and III. A particle cannot penetrate these infinite potential barriers, so the
probability of finding the particle in regions I and III is zero. The time-independent Schrodinger's
wave equation in region II, where V = 0, becomes
2x  2mE(x)  0
(2.27)
2x2 2
A particular form of solution to this equation is given by
A1 cosKx A2 sinKx (2.28)
where

K  2mE (2.29)
2
One boundary condition is that the wave function  (x) must be continuous so that
x 0  x  L  0 (2.30)
Applymg the boundary conditions at x = 0, we must have that A1  0, At x = L, we have
x  L  0  A2 sinKL (2.31)
This equation is valid if KL = n  , where the parameter n is a positive integer, or n = 1,2,3. . . . . The
parameter n is referred to as a quantum number. We can write
K  n (2.32)
L
Negative values of n simply introduce a negative sign in the wave function and yield redundant
solutions for the probability density function. We cannot physically distinguish any difference between
+n and -n solutions. Becausc of this redundancy, negative values of n are not considered. The
coefficient A2 can be found from the normalization boundary condition that was given by Equation
(2.18) as

 xxdx1.


(2.18)

If we assume that the wave function solution  (x) is a real function, then  (x) = x.
Substituting the wave function into Equation (2.18), we have
L
 A sin Kxdx1
0
2
2
2 (2.33)

Evaluating this integral gives

A2  2 (2.34)
L
Finally. the time-independent wave solution is given by

x  2 sin 2nx ; where n = 1, 2, 3, ------ (2.35)

L  L
This solution represents the electron in the infinite potential well and is a standing wave solution.
The free electron was represented by a traveling wave. and now the bound particle is represented by
a standing wave.

The parameter K in the wave solution was defined by Equations (2.29) and (2.32). Equating these two
expressions for K. we obtain

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2mE n22
(2.36)
2 L2
The total energy can be written as

En   2
2 2 2
n
where n = 1, 2, 3, ……. (2.37)
2mL
For the particle in the infinite potential well. the wave function is now given by

x  2 sinKx  2 sin nx (2.38)

L L  L
where the constant K must have discrete values, implying that the total energy of the particle can only
have discrete values. This result means that the energy of the particle is quantized. That is, the
energy of the particle can only have particular discrete values. The quantization of the particle
energy is contrary to results from classical physics, which would allow the particle to have continuous
energy values. The discrete energies lead to quantum states that will be considered in more detail in
this and later chapters. The quantization of the energy of a bound particle is an extremely important
result. The full time dependent wave function is (at time, t, the wave function can be written as)

x, t  2 e  sin nx

i E t n

L  L
Example 2.3

Consider an electron in an infinite potentral well of width 5 Å. Calculate the first three energy levels
of an electron in an infinite potential well.

Solution

From Equation (2.37)

 
En  n  2  n   1.310541010 Js2  n2 2.411019 J
2 2 2 2 2 34
 

2mL 2 9.1110 510 m  
En  n2
2. 

41 1019
19  1.51
eVn2 
1.60210
E1  n21.51eV12 1.51 1.51eV; E2  n21.51eV 22 1.51 6.04eV
E3  n21.51eV32 1.51 13.59eV
Nb. This calculation shows the order of magnitude of the energy levels of a bound electron

Exercise
1. The width of the infinite potential well in Example 2.3 is doubled to 10 Å Calculate the first
three energy levels in terms of electron volts for an electron. (0.376 eV, 1.50 eV, 3.38 eV)

Figure 2.6a shows the first four allowed energies for the particle in the infinite potential well, and
Figures 2.6b and 2.6c show the corresponding wave functions and probability functions. We may note
that as the energy increases, the probability of finding the particle at any given value of x becomes
more uniform.

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Figure 2.6 Particle in an infinite potential well: (a) Four lowest discrete energy levels.
(b) Corresponding wave functions nx. (c) Corresponding probability functions nx2 .
Since the wavefunction in eqn (2.38) is normalized, we have that

2 sin nx . 2 sin nxdx 2 L sin2 nx 1
L


ij dx1 if i  j i.e0 L  L  L  L  L0  L 
 L
2 sin nix. 2 sin njxdx wheren  n
And if i  j ;

 i j 0 L  L  L  L 
 
 dx  i j

Let t 
 x  dt   dx
L L
ij dx L2 0 sinnit.sinnjt.Ldt
 L

Using the identity sinnit.sinnjt cos

1 n n t 1 cosn n t
i j i j
2 2

2  1cosn n t dt  2 1cosn n t dt  0
 i j  0 2 i j

 
 dx 
 0 2 i j

Since sinm  0 for m an integer. We thus have


  dx 0


i j ; fori  j (*)

When eqn (*) holds, we say that i and  j are ORTHOGONAL to each other for i j
fori  j


  dx
 1
0 fori  j
(**)

i j ij

The property of the wave functions illustrated by eqn (**) is called ORTHONORMALITY.

Worked Example

1. Use the orthonormality relation to evaluate the following integrals

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2  2 sin 2x and 5  2 sin 5x

L
Given that
L L L L   dx
0
*
5 2

L L L L
Evaluate (a) 2*2 dx (b) 5*5 dx (c) 2*5 dx (d)   dx
*
5 2
0 0 0 0
Answers (a) 1 (b) 1 (c) 0 (d) 0

2. Explain what is mean by the orthogonality of two wave functions 1(x)and 2 (x)in the
quantum mechanics of a particle on a line  x  
Solution
 
  dx1   dx

*
1 2

*
2 1

Worked Example

The nuclear potential that binds protons and neutrons in the nucleus of an atom is often approximated
by an infinite square well potential. A proton is confined in an infinite square well of width 10 fm.
Calculate the energy and wavelength of the photon emitted when the proton undergoes a transition
from the first excited state (n = 2) to the ground state (n = 1). In what region of the electromagnetic
spectrum does this wavelength belong? h  6.261034 Js, mp 1.671027 kg
 1.0541034Js 1 femtometer = 1015metre.
Solution

The energy En of a particle of mass m in the nth energy state of an infinite square well potential with
width L is given by
2 2
En  h2
n
8mL
The energy E and wavelength  of a photon emitted as the particle makes a transition from the n =
2 state to the n = 1 state are
2 2 2 2 2
hc 2 h
E  E2 E1   2  2  2 1 h 3h
 8mL 8mL 8mL
3h2
E 2  3 6. 
626 34 2
10   1  6.16MeV
8mL 81.671027 101015 1.61019
2
 
 hc 6.62610 Js310
34 8
ms1  202fm
E 6161659 eV1.61019ev/s
Example
Are the particle-in-a box stationary state wave functions, eigenfunctions of px2 ? Where px2 is the
square of 1-D momentum Using equation (2.0)*

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px2  2  2 eiEt/  2 sin nx  n 2 eiEt/  2 sin nx

2 2 2 2

x L  L L L  L

p   2 
2 2 2
2 n
x (2.0)**
L
p2
Hence a measurement of x will always give the result n2h2 / 4L2 when the particle is in the stationary state
with quantum number n. This should come as no surprise: the potential energy in the box is zero, and the
2
p
Hamilitonian is H T V  T 0  p / 2m. We than have H  E   (from eqn
2 x
x )
2m
2 2
px2 2mE  2mn h2  which is in agreement with (2.0)**. The only possible value for px2 is
4L
px2  n2h2 / 4L2

Orthornormal sets

It can be shown mathematically that the eigenfunctions with different eigenvalues are mutually
orthogonal

mndx 0 , if m  n
L
2 sin 2x 2 sin3xdx 0
For example  (x) (x)dx 

2 3
0
 
L  L L L
 
If the eigenfunctions are normalized so that mndx 1, then the eigenfunctions form the
orthonormal set, where,
0 m n

mndx nm  1 m n


 2 sin3x 2 sin3xdx 1
L
For example 3 3

(x) (x) dx
0 L L L L
 

2.3.2.1 THE FINITE POTENTIAL WELL

Consider a particle in the potential

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x L
V0 2
V(x)  
0  x L
L V0  0

V0
2
L
2
x
2

EV0 - Unbound states, total energy E continuous (not quantized); EV0 - bound states,
expect discrete states

Region I L x L
2 2
Solve the TISE

  d (2x)  E(x)  d (2x)  K2(x) where K  2mE

2 2 2

2m dx dx 2
Solutions: 1(x)  AsinKxBcosKx (same as the infinite potential well)
A and B are arbitrary constants
Region II x L
2
In region II, E = KE + PE = KE+ V0  E < V0  KE < 0

  d (2x) V0(x)  E(x)  d (2x) 2(x)

2 2 2

2m dx dx
  2mV02E  0

Solutions II (x)  Ce De
x x

Put D = 0 , otherwise (x) not square integrable (blows up at large positive x.) II (x)  Cex
Region III x L
2
Regions II and III are the same with V= V0
Solutions II (x)  Fe Ge
x x
(like in region II)

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
Put F = 0 , otherwise not square integrable (x) (blows up at large negative x) II (x)  Ge
x

The potential is symmetric w.r.t. to x = 0 

expect symmetric (even-parity) and antisymmetric
(odd-parity) states
Consider even-parity solutions only: 1(x)  BcosKx

Apply general conditions on (x) at x  L/ 2, (x) is continuous at x  L/ 2: 

1(L/ 2) II L/ 2
L
Bcos(KL/ 2)  Ce 2 (1)
The first derivative of (x) must be continuous at x  L/ 2 i.e.
d  (L/ 2)  d  L/ 2
dx 1 dx II
L
BKsin(KL/ 2)  Ce 2 (2)
No new constraints at x = −L/2 since we consider symmetric solutions only. divide equation (2) by
equation (1)

tan KL   (3)

2 K
Introduce   KL  LHS of equation (3) y()  tan and 0  K0L isaconstantwhere
2 2
K0  2mV 0
2
 RHS of equation (3): y()    K02 1  V0 E  02 1
2 2

K K E 
The even-parity solutions are determined when the curve y()  tan intersects the curve y
K
where   KL
2

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bound states with discrete (quantized) energy

Comments:
2 
2 2
larger V0  more bound states;; smaller V0  less bound states, when 0    V0 
mL2
 only one symmetric state exists
 In the Finite potential well (FPW) there is always at least one bound state.
Infinite potential well (IPW): wavenumbers Kn  n or n  n
L 2
(n = 1, 3, 5, ... for symmetric states).
 The wavenumber and energy of the nth state in FPW is less than in the IPW.

The FPW – odd-parity solutions

Consider odd-parity solutions only: 1(x)  AsinKx
Apply general conditions on (x) at x  L/ 2

(x) is continuous at x  L/ 2: 1(L/ 2) II L/ 2
L
Bsin(KL/ 2)  Ce 2 (1.1)
The first derivative of (x) must be continuous at x  L/ 2 i.e.
d  (L/ 2)  d  L/ 2
dx 1 dx II
L
BKcos(KL/ 2)  Ce 2 (1.2)
No new constraints at x = −L/2 since we consider antisymmetric solutions only.
Dividing equation (1.2) by equation (1.1)

cot KL    (1.3)

2 K

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As before introduce   KL  LHS of equation (3) y()  cot and 0  K0L isaconstant
2 2
where K0  2mV 0
2

 RHS of equation (1.3): y()    K02 1   V0 E   02 1

2 2

K K E 
The odd-parity solutions are determined when the curve y()  cot intersects the curve
y 
K
where   KL
2

Figure 4: Wave functions and probability densities of a particle in a finite square potential well.

Comparison of the Finite Potential Well (FPW) and the Infinite Potential Well
(IPW)

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Infinite Potential Well (IPW) Finite Potential Well (FPW)

(x) confined to the well (x) spreads out beyond the well
Kn  n Kn and energies lower
L
Infinite tower of states Finite tower of states
No unbound states Unbound states when EV0
The energy levels in the FPW are lower than those in the IPW because the wavefunction spreads
out (by penetrating the classically forbidden region) and therefore reduces its KE.

2.3.2.1 Applications of the “particle in a box”

Despite its simplicity, the idea of a particle in a box has been applied to many situations with
spectacular success. Three examples suffice.
1. The simplest example of two nucleons bound by the strong nuclear force is the deuteron.
In nature, the deuteron is only barely bound, and has no excited states. Approximating the
nuclear force by a radial square well as shown in figure 4 spectacularly reproduced the existing
knowledge of the deuteron, and provided further insight into the nuclear force. Notice that
only one state exists in the well. The oscillatory part of the wave function in the well barely
“turns over” before the exponential part outside the well commences. The deuteron is indeed
“barely bound” ! The well depth is 35MeV, indicating the strength of the nucleon-nucleon
force. The ground state of the deuteron is a mere 2.2 MeV below the top of the well. If the
nucleon-nucleon force were only slightly weaker, there would be no such thing as the
deuteron, the proton to helium fusion cycle in the sun would not be possible, and the universe
would not have been able evolve beyond hydrogen gas clouds to form burning stars.

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Figure 5: The deuteron radial square well, showing only one weakly bound state, and the
corresponding wave function.

2. The electrons in a metal may be conceived of as particles in a box. The “background” of

positive ion cores provides the attractive three dimensional well in which they move. This
situation is shown schematically in figure 2.6. The electrons are therefore quantum particles
represented by wave functions trapped in the “metal box”. Their energy is given by the
equation 64, adapted for a three dimensional box in an obvious way.

En   2 ;
2 2 2
n n2  nx2 ny2 nz2
2mL
This model is able to explain the motion of conduction electrons, their contribution to the
specific heat of the metal, and their contribution to magnetism in the metal. In addition, the
penetration of the electron wave function outside of the “metal box” is vital in understanding
the propagation of electrons across contacts, even if there is an insulating oxide layer covering
the metal, or even of the contact interface is inhomogeneous.
3. The thermodynamic equilibrium of a cold white dwarf star is modelled by balancing the
behaviour of the electrons, modelled as particles in a box, with the gravitational forces. This
model predicts the stellar mass threshold (Chandrasekhar limit) for final collapse of a white
dwarf to a black hole.

13
Maxwell Mageto, PhD