QM 3: Eigenvalue problem May 30, 2005 1

Chapter 3. The Eigenvalue Problem

3.1. The eigenvalue problem: denition and examples

x 1. Denition. In the previous chapter I told you that in Quantum Me-

chanics the dynamical variables of a system (particle positions, momenta,

energies, etc.) are represented by operators. The word `represented' is delib-

erately vague and it will become more clear as we proceed. To characterize

the motion of a mechanical system we measure how its dynamical variables

change in time. This means that these variables must be real numbers. If

Quantum Mechanics represents these variables by operators, how are we to

measure their values?

The connection between operators and numerical values that we can mea-

sure is provided by the eigenvalue equation

^ =
O (3.1)

^ The function that

Such an equation can be written for any operator O.

satises this equation is called an eigenfunction or eigenstate of the operator

^ `Eigen' is German for `own', as in \the operator's own function". The

O.

^ In this equation O
number is called an eigenvalue of O. ^ is known, and
QM 3: Eigenvalue problem May 30, 2005 2

and are to be found.

The connection between the eigenvalues of an operator and the results

of a measurement will be explained in Chapter 4. In Chapter 5 you will

learn how to extract physical information from the eigenfunctions. In this

chapter I will explain what an eigenvalue problem is and state some of the

properties of eigenvalues and eigenfunctions. A thorough understanding of

the eigenvalue equation requires more time and more mathematics than is

available to us. Because of this, we will learn by examining a few simple

examples.

x 2. The eigenvalue problem for p^x . Following the general denition (3.1),

the eigenvalue equation for the operator p^x is

p^x(x; y; z) = p(x; y; z) (3.2)

Here (x; y; z) is a function of coordinates (an eigenfunction of p^x )and p is

a number (an eigenvalue of p^x ). The operator p^x was dened in Chapter 2,

x12, and is given by

h
@
p^x = (3.3)
i @x

Using this in Eq. 3.2 leads to the eigenvalue equation

h
@
= p (3.4)
i @x
QM 3: Eigenvalue problem May 30, 2005 3

Here p and are unknown and we need to nd them by solving this equation.

You can check easily that

= exp[ikx]

is a solution of Eq. 3.4. Indeed, inserting exp[ikx] in Eq. 3.4 gives

h
@ ikx h

p^x eikx = e = (ik)eikx = h
keikx (3.5)
i @x i

If you compare Eq. 3.2 with Eq. 3.5, you see that (x) exp[ikx] is an

eigenfunction of p^x with the eigenvalue p = h

k.

x 3. p^x has an innite number of eigenvalues. The eigenvalue equation Eq. 3.4

puts no restriction on the value of p = h

k: exp[ikx] is an eigenfunction and

h
k is the corresponding eigenvalue for any number k, be it real or complex.

There are as many eigenvalues and eigenfunctions of p^x as there are complex

numbers.

^ (i.e. if O
Moreover, if is an eigenfunction of a linear operator O ^ = o,

where o is a number), then (where can be any complex number) is also

^ corresponding to the same eigenvalue o. To see that

an eigenfunction of O,

^ and use the fact

this is true, introduce into the eigenvalue equation for O

^ = o and O
that O ^ ^
= O.
QM 3: Eigenvalue problem May 30, 2005 4

It is not unusual that a mathematical equation describing a physical phe-

nomenon has more than one solution and that not all of them have a physical

meaning. As you'll see soon, physics provides additional conditions that a

physically relevant eigenfunction must satisfy.

Exercise 3.1 Show that exp[ikx], exp[ikx], exp[kx], exp[kx] (where k is

a real number) are eigenstates of p^x . Calculate the corresponding eigenvalues.

Exercise 3.2 Show that (x; y; z) = exp[i(kxx + ky y + kz z)] eikr

(where the vector k has the Cartesian components fkx ; ky ; kz g and r has the

Cartesian components fx; y; zg) is an eigenstate of p^x with the eigenvalue

hkx and an eigenstate of p^y with the eigenvalue hky and an eigenstate of

p^z with the eigenvalue hkz .

Exercise 3.3 Show that sin(kx x) sin(ky y) sin(kz z) is an eigenstate of p^2x +

2 kx2 + ky2 + kz2 .
p^2y + p^2z with eigenvalue h

Exercise 3.4 Show that exp[ik r] is an eigenstate of p^2x + p^2y + p^2z .

x 4. The eigenvalue problem for angular momentum. I examine the eigen-

value problem for angular momentum to give another simple example, which
QM 3: Eigenvalue problem May 30, 2005 5

has interesting features that are encountered in other problems in Quantum

Mechanics.

In Chapter 2, x15, I postulated that the operators corresponding to the

components of the angular momentum vector are:

!
^x = h
L

y
@
z
@
(3.6)
i @z @y
!
^y = h
@ @
L x z (3.7)
i @z @x
!
^ h
@ @
Lz = x y (3.8)
i @y @x

I will discuss later the physical interpretation of these operators. For now I

examine briey some properties of their eigenvalues. According to the general

^ z is
denition (Eq. 3.1), the eigenvalue problem for L

^ z (x; y; z) = `z (x; y; z)
L (3.9)

^ z (see Eq. 3.8) turns Eq. 3.9 into

Using the denition of L
!
h
@ @
x y = `z (3.10)
i @y @x

The eigenfunction (x; y; z) and the eigenvalue `z are calculated by solving

this equation.

The eigenvalue equation for the square of the angular momentum is

^ 2 (x; y; z) = (x; y; z)
L (3.11)
QM 3: Eigenvalue problem May 30, 2005 6

^ 2 from
You can calculate L

^ 2 = L
L ^ xL
^ x + L
^y L
^y + L
^zL
^z

^ x, L
and Eqs. 3.6{3.8,which give expressions for L ^ y , and L
^z .

Exercise 3.5 Show that (see WorkBookQM.3, Cell 2)

^ 2 L
L ^ L
^ =

leads to
"
2 @ @2 @ @2 @2
h 2z + (x2 + y 2 ) 2 2y 2yz + (x2 + z 2 ) 2
@z @z @y @y@z @y
#
2 2 2
@ @ @ @
2x 2xz + 2xy + (y 2 + z 2 ) 2 = `
@x @x@z @x@y @x

x 5. If two operators commute, they have the same eigenfunctions. Let us

examine the following examples of eigenfunctions (see WorkBookQM.3, Cell

3):
x + iy
1 (x; y; z) = p 2 (3.12)
x + y2 + z 2
x iy
2 (x; y; z) = p 2 (3.13)
x + y2 + z 2

and
z(x + iy)
3 (x; y; z) = (3.14)
x2+ y2 + z 2
QM 3: Eigenvalue problem May 30, 2005 7

They satisfy the equations

^ z 1 (x; y; z) = h
L 1 (x; y; z)

^ z 2 (x; y; z) = h2 (x; y; z)
L

^ z 3 (x; y; z) = h
L 3 (x; y; z)

and

^ 2 (x; y; z) = h
L 2 (x; y; z) for = 1; 2; 3 (3.15)

^ z and L
This means that 1 , 2 , and 3 are eigenfunctions of both L ^ 2 . While

the two operators have common eigenfunctions they have dierent eigenval-

ues.

One can prove the following general theorem: If two linear operators A^

^ commute, we can always construct joint eigenfunctions of A^ and B.

and B ^

Conversely if two linear operators have the same eigenfunctions then they

commute.

By denition (see Chapter 2, x7), two operators commute if

(AB BA) = 0

for any function that is acceptable in Quantum Mechanics (see Section 3.2

for the meaning of `acceptable').

QM 3: Eigenvalue problem May 30, 2005 8

As you'll see later, this rule is very important because if two dynamical

variables (e.g. p^x and V^ ) do not commute, their values cannot be measured

simultaneously in an experiment, and measuring one of them changes the

value of the other. An example of this behavior is the Heisenberg Uncertainty

Principle, which says that position and momentum cannot be measured si-

multaneously. One can show that this happens because the coordinate and

the momentum operators do not commute.

Exercise 3.6 Show that if two operators have the same eigenvalues, then

their commutator is zero when it is applied to one of the common eigenvalues.

Exercise 3.7 Show that if A^ and B

^ are two linear operators and A
^ = a

^ B]
and [A; ^ = 0, then B
^ is also an eigenfunction of A,
^ with the eigenvalue

a.

Exercise 3.8 Verify that 1 (x; y; z) = (x + iy)=r, 2 (x; y; z) = (x iy)=r,

^ z and L
and 3 (x; y; z) = z(x + iy)=r2 are eigenfunctions of both L ^ 2 where
p 2
r = x + y 2 + z 2 . Calculate the corresponding eigenvalues (see Work-

BookQM.3, Cell 2).

x 6. Degenerate eigenvalues. The functions

x + iy
1 (x; y; z) = p 2 (3.16)
x + y2 + z 2
QM 3: Eigenvalue problem May 30, 2005 9

x iy
2 (x; y; z) = p 2 (3.17)
x + y2 + z 2

satisfy the equations

^ 2 1 (x; y; z) = h
L 2 1 (x; y; z) (3.18)

and

^ 2 2 (x; y; z) = h2 2 (x; y; z)
L (3.19)

You can test that this is true by inserting the expressions Eqs. 3.16 and 3.17

in Eqs. 3.18 and 3.19 (see Cell 3 of WorkBookQM.3).

Eqs. 3.18 and 3.19 indicate that 1 , 2 are eigenfunctions of the operator

^ 2 that correspond to the same eigenvalue h

L 2 . When several eigenfunctions

have the same eigenvalue, we say that they are degenerate.

Degenerate eigenfunctions appear frequently in Quantum Mechanics and,

as you'll see later, degeneracy has a physical interpretation. According to

Webster the adjective degenerate means \a: having declined (as in nature,

character, structure, or function) from an ancestral or former state b : having

sunk to a condition below that which is normal to a type; especially : having

sunk to a lower and usually corrupt and vicious state". I am unable to

imagine why the person who named this property found it so oensive and
QM 3: Eigenvalue problem May 30, 2005 10

morally repulsive. These poor functions are stuck with the demeaning name,

and the prospect of naming them dierently to clear their reputation are very

dim.

You can also show easily (see Cell 3 of WorkBookQM.3) that 1 and 2

satisfy the equations

^ z 1 (x; y; z) = h
L 1 (x; y; z) (3.20)

and

^ z 2 (x; y; z) = h2 (x; y; z)
L (3.21)

^ z , corresponding
which indicate that 1 and 2 are also eigenfunctions of L

and h, respectively.
to the eigenvalues h

^ 2 are degenerate. The

We can now understand why the eigenvalues of L

^ 2 and L
functions 1 (x; y; z) and 2 (x; y; z) are eigenvalues of both L ^ z . These

two operators are related: one gives the square of the length of the angular

momentum vector and the other gives the projection of the angular momen-

tum vector on the OZ axis. From classical mechanics we know that the length

of the angular momentum squared is proportional to the rotational energy of

the particle; the projection of the angular momentum vector on the OZ axis

tells us the orientation of the axis of rotation. Since the eigenstates 1 (x; y; z)
QM 3: Eigenvalue problem May 30, 2005 11

^ 2 , they describe states

and 2 (x; y; z) correspond to the same eigenvalue of L

in which the particle has the same rotational energy. If the particle in the

states 1 (x; y; z) has the same rotational energy as a particle in the state

2 (x; y; z), why are these states dierent? The answer is given by Eqs. 3.20

and 3.21, which tell us that the two states correspond to particles having

^ z , which means that their axis of rotation has a

dierent eigenvalues of L

dierent orientation.

^ are
This behavior is general. The degenerate states of an operator O

usually non-degenerate states of another operator. In the example given

^ 2 are non-degenerate states of L.

above, the degenerate states of L ^

x 7. A summary of some of the observations made so far. The particular

cases studied so far have revealed behavior that is general and must be re-

membered.

An eigenvalue problem does not have a unique solution. As you have seen

^ z , and L
in x3 and x5 the operators p^x , L ^ 2 all have more than one eigenfunc-

tion. This is true for all operators encountered in Quantum Mechanics. In

many cases the number of eigenfunctions is innite.

Two dierent operators can have common eigenfunctions, but with dif-

ferent eigenvalues. This means that given two linear operators A^ and B,
^ it
QM 3: Eigenvalue problem May 30, 2005 12

^ = a and B
is sometimes possible to nd a function such that A ^ = b.

For example, exp[ikx] is an eigenfunction of p^x with the eigenvalue hk

2 k 2 =2m. The general

and an eigenfunction of p^2x =2m with the eigenvalue h

rule is that two operators have the same eigenfunctions if and only if they

commute.

Finally, we have seen that sometimes an operator has several eigenfunc-

tions that correspond to the same eigenvalue. For example, exp[ikx] and

exp[ikx] are eigenfunctions of p^2x =2m; they both correspond to the eigenvalue

2 k 2 =2m (show that this is true). When this happens, the eigenvalue is called
h

degenerate.

3.2. Which eigenfunctions have a meaning in physics?

x 8. Not all eigenfunctions are physically meaningful. So far we have looked

at the eigenvalue problem as a mathematical problem. It often happens that

some of the solutions of an equation that represents a physical process have

no physical meaning and need to be discarded. This is true in the case of

the eigenvalue problem.

x 9. Normalization. To select those eigenfunctions that describe the physical

QM 3: Eigenvalue problem May 30, 2005 13

properties of a system, we must impose additional conditions. One of them

is written in terms of the symbol

Z +1 Z +1
hji dr(1) dr(N ) (r(1); : : : ; r(N ))(r(1); : : : ; r(N ))
1 1

(3.22)

which is called the scalar product of with . Here dr(k) dx(k) dy(k) dz(k)

and x(k); y(k); z(k) are the coordinates of particle k, located at r(k). (r(1); : : : ; r(N ))

is the complex conjugate of (r(1); : : : ; r(N )).

The physical interpretation of the eigenfunctions of an operator repre-

senting a dynamical variable (momentum, kinetic energy, total energy, . . . )

requires that they must satisfy the normalization condition

Z +1 Z +1
hji dr(1) dr(N ) (r(1); : : : ; r(N ))(r(1); : : : ; r(N )) = 1
1 1

(3.23)

A function that satises Eq. 3.23 is called normalized.

The condition in Eq. 3.23 follows from the physical interpretation of eigen-

functions, which postulates that

(r(1); : : : ; r(N ))(r(1); : : : ; r(N ))dr(1) dr(N)

is the probability that the particle labeled 1 is in the volume element dr(1),

centered around the point r(1), the particle labeled 2 is in the volume element
QM 3: Eigenvalue problem May 30, 2005 14

dr(2), centered around the point r(2), . . . . The integral in Eq. 3.23 is the

probability that the particles are located somewhere in space, and this must

be equal to one.

x 10. A relaxed condition. This seems to be a very stringent mathematical

condition. However, we can relax it considerably based on the following

observation. Suppose that satises the eigenvalue equation of a linear

^
operator O:

^ =
O

Dene = C where C is an arbitrary complex number. Then the function

^ with the eigenvalue :

is also an eigenfunction of O

^ = O(C)
O ^ ^ = C() = (C) =
= C(O)

Why is this of any help to us? Let us assume that we have found an

^ with the eigenvalue , so that O

eigenfunction of O ^ = , but does not

satisfy the normalization condition (3.23). This does not mean that we need

to throw this function away and look for one that is normalized. We can use

the procedure described below to turn into a normalized eigenfunction.

QM 3: Eigenvalue problem May 30, 2005 15

Assume that satises the weaker condition

Z +1 Z +1
hji = dr(1) dr(N ) (r(1); : : : ; r(N ))(r(1); : : : ; r(N)) = M
1 1

(3.24)

where M is some positive real number. The specic value of M is irrelevant

for what follows; what counts is that h; i is not innite (it is easy to show

that it is real and positive). The function

p (3.25)
M

^ with the eigenvalue , and it is normalized.

is also an eigenfunction of O,

^ and hji.
This statement is very easy to check by evaluating O

By this procedure, we turn the eigenfunction into the physically ac-

ceptable eigenfunction . We say that we have normalized , or that is

the normalized version of .

We can now replace the normalization condition (3.23) with the weaker

condition (3.24), with the proviso that if we obtain an eigenfunction that

satises Eq. 3.24 then the physically meaningful eigenfunction is given by

Eq. 3.25. You will see soon an example using this idea.
QM 3: Eigenvalue problem May 30, 2005 16

3.3. An example: the eigenfunctions of kinetic energy

x 11. The fact that mathematics provides more solutions than are needed by

physics is not unusual. This is not a great nuisance, as long as we have a cri-

terion that allows us to pick the solutions we want. In Quantum Mechanics,

the condition in Eq. 3.24 is often sucient.

There are cases in which additional conditions are necessary. These are

not general, but follow from an examination of the physics of the specic

system. The eigenfunctions of the kinetic energy operator provide an example

of this sort.

x 12. One-dimensional motion in the force-free, unbounded space. We study

the case of a particle moving in one dimension, to examine why we need

such additional conditions, to show what these conditions are, to explain

how they are used, and to indicate how they aect the eigenvalues and the

eigenfunctions.

We assume that no force acts on this particle and it moves in an un-

bounded space. In other words, this particle is alone in the universe. Since

no force acts on the particle, its total energy is equal to its kinetic energy.
QM 3: Eigenvalue problem May 30, 2005 17

x 13. The eigenfunctions of the kinetic energy operator. The eigenvalue prob-

lem for the kinetic energy operator is

^
K(x) = K(x) (3.26)

^ = p^2 =2m = (h2 =2m)(@ 2 =@x2 ),

Since, for a one-dimensional system, K

Eq. 3.26 becomes

2 @ 2 (x)
h
= K(x) (3.27)
2m @x2

This is a well-known dierential equation. The following functions satisfy

it: exp[kx]; exp[kx]; sin(kx); cos(kx); exp[ikx]; exp[ikx]. I will verify this

statement for (x) = exp[kx]. I have @=@x = k exp[kx] and @ 2 =@x2 =

k 2 exp[kx]. Inserting this in Eq. 3.27 leads to

2 k 2 kx
h
e = Kekx
2m

Dividing by exp[kx] gives K = h2 k 2 =2m. Therefore (x) = exp[kx] is an

^ with eigenvalue K = h2 k 2 =2m. In WorkBookQM.3,

eigenfunction of K

Cell 4, I show that all the functions listed above are eigenfunctions. Their

eigenvalues are given in Table 3.1.

x 14. More general eigenfunctions. The eigenfunctions sin(kx) and cos(kx)

2 k 2 =2m. If two
are degenerate: they correspond to the same eigenvalue h
QM 3: Eigenvalue problem May 30, 2005 18

(x) sin(kx) cos(kx) eikx eikx ekx ekx

^ h2
k2 h2
k2 h2
k2 h2
k2 2 2 2 2
K= 2m 2m 2m 2m
k2m
h

k2mh

Table 3.1: Eigenfunctions and corresponding eigenvalues (for simplicity, I

^
constrain k to be a real number) for the kinetic energy operator K.

^ having the
functions 1 and 2 are eigenfunctions of a linear operator O

same eigenvalue , then for any complex (or real) numbers A and B, the

^ with the
function (x) A1 (x) + B2 (x) is also an eigenfunction of O,

eigenvalue . To put this in symbols, if

^ 1 = 1
O

and

^ 2 = 2 ;
O

and

(x) = A1 (x) + B2 (x);

then

^ =
O

^
You can easily see that this follows from the linearity of O:

^ = O(A
O ^ ^ ^
1 +B2 ) = AO1 +B O2 = A1 +B2 = (A1 +B2 ) =
QM 3: Eigenvalue problem May 30, 2005 19

This `combining' property for degenerate eigenvalues is general. Let us

use it for the eigenfunctions sin(kx) and cos(kx) of the kinetic energy oper-

ator. The conclusion is that

1 (x) = A1 sin(kx) + B1 cos(kx) (3.28)

^ with the eigenvalue K = k 2h

is an eigenfunction of K, 2 =2m.

Similarly

2 (x) = A2 eikx + B2 eikx (3.29)

^ with the eigenvalue K = k 2h

is an eigenfunction of K, 2 =2m. And

3 (x) = A3 ekx + B3 ekx (3.30)

^ with the eigenvalue K = k 2 h

is an eigenfunction of K, 2 =2m.

Exercise 3.9 Show that 1 and 2 dened by Eqs. 3.28 and 3.29 are not

independent: for a proper choice of C and D, 1 (x) = A1 sin(kx)+B1 cos(kx)

is the same function as C exp[ikx] + D exp[ikx].

x 15. Which of these eigenfunctions can be normalized? We need now to

establish which of these eigenfunctions and eigenvalues are physically ac-

ceptable. This means that we will test which one satises the condition in

Eq. 3.24.
QM 3: Eigenvalue problem May 30, 2005 20

For the eigenfunction (x) = sin(kx), the normalization condition re-

quires that

Z +1 Z +1
hji = dx (x)(x) = dx sin2 (kx) = M < 1
1 1

It is easy to see that this integral is not nite. Indeed (see your calculus book

or use Mathematica)

Z +z
sin(2kz)
sin2 (kx)dx = z
z 2k

and this expression is not nite as z becomes innite.

The function (x) exp[ikx] doesn't fare better:

Z +1 Z +1
hji = dx exp[ikx] exp[ikx] = dx
1 1

Another integral that is not nite, and another eigenfunction to be thrown

away.

We come at last to (x) exp[kx]:

Z +1 Z +1
exp[2k1] exp[2k1]
hji = dx exp[kx] exp[kx] = e2kx dx = =1
1 1 2k 2k

This integral is not nite, so it does not satisfy Eq. 3.24.

If sin(kx), exp[ikx], and exp[kx] do not satisfy Eq. 3.24, neither will

1 , 2 , or 3 from Eqs. 3.28{3.30. None of the eigenfunctions I found for

QM 3: Eigenvalue problem May 30, 2005 21

^ is physically meaningful. This is distressing and mathematics gives us

K

no relief, since we have exhausted all eigenfunctions. The solution to this

dilemma must come from physics.

x 16. Boundary conditions: the particle in a box. We have run into trouble

because our formulation of the problem misses an important aspect of the

physics of the problem. Any particle on which we perform an experiment is

conned inside an apparatus. This means that the probability of nding the

particle outside the apparatus is zero.

Let us assume that in our one-dimensional problem, the walls of the

apparatus are at x = 0 and x = L. As long as the coordinate of the particle

satises

0xL

the particle is inside the machine. Since the particle cannot escape from the

machine, the probability (x)(x) that the particle is outside the \box" is

zero. This means that we must look for a solution of the eigenvalue equation

for the kinetic energy, that satises the condition

j(x)j2 = 0 if x < 0 or x > L (3.31)

This condition must be imposed in addition to the normalization condition

QM 3: Eigenvalue problem May 30, 2005 22

Eq. 3.24.

Furthermore, we impose the additional condition that the wave function

must be continuous. You can see that this is a reasonable condition: the

momentum operator cannot be applied to a discontinuous function, because

such a function does not have a derivative.

Because of the continuity requirement, the function (x) must also satisfy

(x = 0) = 0 (3.32)

and

(x = L) = 0 (3.33)

In the theory of dierential equations these are called the boundary con-

ditions, because they force the eigenfunction to take certain values at the

boundaries x = 0 and x = L.

x 17. Force the eigenfunctions to satisfy the boundary conditions. Let us see

what the boundary conditions do to the eigenfunction 1 dened in Eq. 3.28.

For x = 0, I must have

1 (0) = A sin(k 0) + B cos(k 0) = 0 (3.34)

and for x = L,

1 (L) = A sin(kL) + B cos(kL) = 0 (3.35)

QM 3: Eigenvalue problem May 30, 2005 23

Because sin(k 0) = 0 and cos(k 0) = 1, Eq. 3.34 gives

B=0

Using this in Eq. 3.35 leads to

A sin(kL) = 0 (3.36)

One of the solutions of this equation is A = 0. This is unacceptable: if

A = 0 and B = 0 then 1 0 which makes no sense; it would imply that

the probability of nding the particle anywhere in the box is zero.

If A 6= 0, Eq. 3.36 becomes sin(kL) = 0, which has the solutions

kn = n; n = 0; 1; 2; : : : (3.37)
L

This is very interesting. Before we imposed the boundary conditions (3.32)

and (3.33), sin(kx) satised the eigenvalue equation and the eigenvalue was

2 k 2 =2m. There was no constraint on the values of k: sin(kx) and h

h 2 k 2 =2m

^ for any value of k. When we

were eigenfunctions and eigenvalues of K

impose the boundary conditions, k can no longer take arbitrary values; the

only acceptable values of k are given by Eq. 3.37. As a consequence, the

^ can only take the discrete values

eigenvalues of the kinetic energy operator K

2 kn2
h 22 2
h
Kn = = n ; n = 0; 1; 2; : : : (3.38)
2m 2mL2
QM 3: Eigenvalue problem May 30, 2005 24

The corresponding eigenfunctions are

8
>
>
> n
< A sin L
x if 0 x L
n (x) = (3.39)
>
>
>
: 0 if x 0 or x L

Note that we use the subscript n to label the eigenfunctions and the eigen-

values.

x 18. Quantization. As you will learn soon, if I measure the kinetic energy of

a particle I will obtain one of the eigenvalues of the kinetic energy operator.

For the example of the particle in an one-dimensional box this means that

h2 2 =2mL2 ) 12 or (
the result of the measurement can be ( h2 2 =2mL2 ) 22

or any other discrete value given by Eq. 3.38. No other value is allowed by

Quantum Mechanics. This is the famous quantization postulated by Planck

and Bohr in the early days of quantum theory.

This quantization appears in our calculation because we conned the

particle in a box. If the box size L or the mass m is large, the allowed values

of the kinetic energy are so close to each other that our instruments are not

good enough to resolve the dierence. In such a case it appears to us that the

kinetic energy can take continuous values, as specied by Classical Mechanics.

We can play billiards without a conict with Quantum Mechanics.

Exercise 3.10 Calculate Kn for n = 1; 2 when m = 1 gram and L = 1 mm.

QM 3: Eigenvalue problem May 30, 2005 25

Is any experiment suciently accurate to measure the dierence K2 K1 ?

x 19. The particle cannot have zero kinetic energy. Another curiosity is pro-

vided by the case n = 0. The eigenfunction corresponding to n = 0 is

0
0 (x) = A sin x =0
L

We must discard this because j0 (x)j2 is identically zero; for this eigenfunc-

tion, the probability that the particle is in the box is zero and this conclusion

is not acceptable, unless you believe in ghosts.

Since we discard 0 (x) as unacceptable, we also discard the energy K0 = 0

as impossible. The smallest kinetic energy the particle can have is K1 . If you

remember that in classical physics the kinetic energy is mv 2 =2, the fact that

the lowest kinetic energy is not zero means that the particle cannot have zero

velocity. This is very strange: the particle in a box can never be at rest! On

the other hand we have all seen that any large, classical object put in a box

does not move if we don't act on it with a force. It appears that Quantum

Mechanics is wrong if the object is large. How can we have two mechanics,

one for small object and one for the large ones? And what happens to the

objects in between, that are neither very large nor very small?

This apparent paradox is easily resolved. If the product mL is very large

QM 3: Eigenvalue problem May 30, 2005 26

2 , the lowest kinetic energy K1 = h

compared to h 2 12 2 =2mL2 is so small

that our instruments cannot determine that it is dierent from zero. This is

why classical physics does not appear to be in error.

Exercise 3.11 Calculate the value of K1 for m = 1 gram and L = 1 cm. Try

to explain why none of our instruments could measure such a small kinetic

energy. Assume that you can dene a velocity v by equating K1 with mv 2 =2.

Calculate how large this velocity is and explain why we could not measure

it.

Exercise 3.12 Show that the function 2 (x) dened by Eq. 3.29 leads to

the same eigenfunctions and eigenvalues as does the function 1 (x) dened

by Eq. 3.28.

Exercise 3.13 Assume that the particle is in a box whose boundaries are

located at
L L
x
2 2

Show that the eigenfunctions look dierent from those derived above (where

the position of the box was dened by 0 x L) but the eigenvalues are

the same. The two boxes are the same except that the second box is the
QM 3: Eigenvalue problem May 30, 2005 27

rst box translated a distance L=2 to the left. Should any of the physically

measurable results for the two boxes be dierent?

Exercise 3.14 The function 3 (x) A3 exp[kx] + B3 exp[kx] is an eigen-

^ Determine A3 and B3 so that 3 satises the boundary conditions

state of K.

(3.32) and (3.33). (Hint: the boundary conditions can be satised only if k is

imaginary. If k is imaginary then 3 is the same as A exp[ikx]+B exp[ikx].)

x 20. Imposing the boundary conditions removes the trouble we had with nor-

^ obtained by impos-
malization. It is easy to see that the eigenfunctions of K

ing the boundary conditions can be normalized. Indeed (see WorkBookQM.3,

Cell 6)

Z +1 Z L " #
2 2 2 nx L L sin(2n)
jn (x)j dx = A sin dx = A2
1 0 L 2 4n

The rst equality follows because n (x) = 0 for x < 0 or x > L and n (x) =

A sin(nx=L) for x 2 [0; L] (see Eq. 3.39). Because sin(2n) = 0, the integral

is equal to A2 L=2. This is nite and therefore the normalization condition

(Eq. 3.24) is satised with M = A2 L=2.

We can normalize the eigenfunction in Eq. 3.39 by using Eq. 3.25. This
QM 3: Eigenvalue problem May 30, 2005 28

leads to the normalized eigenfunctions

8
> 1=2
>
>
< 2 L
sin nxL
if 0 x L
n (x) = (3.40)
>
>
>
: 0 if x 0 or x L

The corresponding eigenvalues are

2
2 kn2
h 2 n
h
Kn = = ; n = 1; 2; : : : (3.41)
2m 2m L

The eigenfunctions corresponding to n and n dier by the constant fac-

tor 1 (i.e. n (x) = n (x)) and therefore they correspond to the same

physical state. For this reason, we consider only positive values of the index

n.

We will come back in a future chapter to this example, to bring out the

physics contained in this result. Its purpose, so far, has been to illustrate

how one solves an eigenvalue problem and to point out how important the

boundary conditions are.

x 21. Some properties of eigenvalues and eigenfunctions. I conclude this

section by pointing out two general properties of the eigenvalue problems

that appear in Quantum Mechanics.

The eigenvalues of the operators appearing in Quantum Mechanics are

always real numbers. This is important because | as you will learn in the
QM 3: Eigenvalue problem May 30, 2005 29

next chapter | the eigenvalues of these operators correspond to physical,

measurable quantities. Therefore, they must be real numbers.

Another important property is that if n (r(1); : : : ; r(N)) and m (r(1); : : : ; r(N ))

^ representing a physical quantity (e.g.

are eigenfunctions of an operator O

energy, momentum, angular momentum) that correspond to two dierent

eigenvalues, then their scalar product is zero:

Z +1
hji n (r(1); : : : ; r(N))m (r(1); : : : ; r(N))dr(1) dr(N ) = 0
1

(3.42)

Two functions satisfying this condition are said to be orthogonal. A set

^
1 (r(1); : : : ; r(N )); 2 (r(1); : : : ; r(N)); : : : of eigenfunctions of an operator O

satisfying Eqs. 3.23 and 3.42 are said to form an orthonormal set. Unlike the

normalization condition, which we must impose, the orthogonality condition

comes free: the operators representing dynamical variables are such that

their eigenfunctions corresponding to dierent eigenvalues are automatically

orthogonal.

Let us check whether this is true for the eigenfunctions (Eq. 3.40) of the
q
kinetic energy operator. We have n (x) = 2=L sin(nx=L) for 0 x L

and n (x) = 0 otherwise. For m 6= n we have (see WorkbookQM.3, Cell 7)

Z +1
hn jm i = n (x)m (x)dx
1
QM 3: Eigenvalue problem May 30, 2005 30

Z L
2 nx mx
= dx sin sin
0 L L L
sin((m n)) sin((m + n))
=
mn m+n
sin((mn)) sin((m+n))
Since m and n are positive integers and m 6= n, mn
= m+n
=0

and the orthogonality condition is satised.

^ is an operator, the equation

x 22. Summary. If O

^ = ;
O

where is a number and is a function, is called the eigenvalue equation for

^ The function satisfying this condition is called an eigen-

the operator O.

^ and the number is the eigenvalue

function or eigenstate of the operator O,

associated with that eigenfunction.

For the operators that appear in Quantum Mechanics, this equation has a

^ represents
large number of solutions, labeled n (r(1); : : : ; r(N)) and n . If O

a dynamical variable, then n is a real number.

Only normalized eigenfunctions, satisfying

Z +1
hji = dr(1) dr(N)n (r(1); : : : ; r(N ))n (r(1); : : : ; r(N)) = 1;
1

have physical meaning. However, we can impose the less stringent condition
Z +1
hji = dr(1) dr(N )n (r(1); : : : ; r(N))n (r(1); : : : ; r(N )) = M < 1
1
QM 3: Eigenvalue problem May 30, 2005 31

If this condition is satised for an eigenfunction , then function dened

by

= p = q
M hji

is a normalized eigenfunction of the same operator, corresponding to the

same eigenvalue as .

In addition, we often must impose boundary conditions, to select physi-

cally meaningful solutions.