Basic Postulates of Quantum Mechanics

September 20, 2012 15:38 BC 8534 - 9in x 6in Quantum Mechanics 2nd Edition
Chapter 3
Basic Postulates of Quantum
Mechanics
3.1 Basic Postulates of Quantum Mechanics
We have introduced two concepts: (i) the state of a particle or a quan-
tum mechanical system is described by a wave function or state function
(r, t) which satises Schrodinger equation; (ii) the dynamical variables
like momentum p and energy E are operators.
Now important properties of a physical system are quantities like p, E
which can be measured or observed; such quantities are called observables.
There must be a means of predicting the values of observables from the
state function and the procedure for doing this is given by following set of
postulates:
(1) To every observable there corresponds an operator

A.
(2) The possible result of a measurement of an observable is one of the
eigenvalues a
n
of

A given by the equation
Au
n
= a
n
u
n
(3.1)
where

A is an operator and a
n
is eigenvalue corresponding to eigen-
function u
n
.
(3) A measurement of

A on a system in an eigenstate certainly leads
to the result a
n
, the eigenvalue.
(4) The average value of a large number of measurements of an ob-
servable on a system described by an arbitrary state is given
by
A a
a =
_

Adr (3.2)
provided that
_

dr = 1, and there exist suitable boundary conditions.

Thus for example, the average value of momentum in x-direction for a state
33
34 Quantum Mechanics
(x, t) is given by
p =
_

(x)
_
i

x
_
(x)dx. (3.3)
Applying to the special case of

A = x, we get the average value of position
x =
_

(x) x(x)dx
=
_
x
dx =
_
x|(x)|
2
dx. (3.4)
This is consistent with our interpretation of (x), that |(x)|
2
determines
the probability density P(x) of the particle in space, since |(x)|
2
appears
as the weighing factor appropriate to x in the calculation of the average
position.
It is convenient to introduce a compact notation for the matrix element
(|
A) or |
A| to mean
_

Adr. Furthermore, the integration may
not always be over space and it may be necessary to imply integration over
other continuous or discontinuous variables.
3.2 Formal Properties of Quantum Mechanical Operators
The quantum mechanical operators (observables) possess certain properties
which are important and we discuss some of them briey.
(a) They are linear, i.e. if (C
n
are numbers)
=
n
C
n
n
(3.5)
then we have
A =
n
C
n

A
n
(3.6)
(b) They obey the laws of association and distribution. Thus if

A,

B
and

C are three operators, we have
A(

B

C) = (

A
B)
C , (3.7)
A(

B +

C) =

A
B +

A
C . (3.8)
(c) An observable corresponds to a hermitian operator. We dene the
hermitian conjugate or adjoint

A
of an operator

A by the equation
(|
A) = (|
= (

A
|) (3.9)
Basic Postulates of Quantum Mechanics 35
i.e.
_

Adr =
_
(

A
dr .
An operator is said to hermitian if

A
=

A, i.e.
(|
A) = (|
A)
= (

A|) . (3.10)
Theorems:
(i) The eigenvalues of a hermitian operator are real.
(ii) The eigenfunctions of a hermitian operator corresponding to dif-
ferent eigenvalues are orthogonal:
We have eigenvalue equation
Au
n
= a
n
u
n
(3.11)
and then
u
m
|
Au
n
= a
n
u
m
|u
n
= a
n
u
n
|u
m
. (3.12)
But from Eq (3.9):
u
m
|
Au
n
= u
m
|
u
n
= u
n
|
Au
m
= a
m
u
n
|u
m
. (3.13)
Hence from Eqs (3.12) and (3.13):
(a
m
a
n
)u
n
|u
m
= 0.
Therefore if
i) m = n, a
n
= a
n
, since u
n
|u
n
= 0 (3.14)
ii) m = n, u
n
|u
m
=
_
u
n
u
m
dr = 0. (3.15)
If the eigenfunctions are normalized,
u
n
|u
n
=
_
u
n
u
n
dr = 1. (3.16)
Hence Eqs (3.15) and (3.16) can be written in a compact form :
u
n
|u
m
=
_
u
n
u
m
dr =
mn
(3.17)
where
_
mn
= 0 m = n,
mn
= 1 m = n.
(3.18)
mn
is called the Kronecker delta. The eigenfunctions are then said to be
orthonormal.
(d) The eigenfunctions u
n
of a hermitian operator (observable) form a
complete orthonormal set so that any arbitrary state function can be
expanded in terms of them, i.e.
=
n
C
n
u
n
. (3.19)
This is what we mean by a complete set. The Eq. (3.19) is called to the
superposition principle, a basic ingredient of quantum mechanics.
Now in analogy with vector analysis where we express a vector in terms
of basis vectors i, j, k, the u
n
s are called basis vectors and C
n
the corre-
sponding coordinates. It follows that
_
u
m
dr = (u
m
|)
=
n
C
n
(u
m
|u
n
)
=
n
C
n
mn
= C
m
, (3.20)
where C
m
is related to the probability of nding the system described by
state in an eigenstate u
m
. Thus
|C
m
|
2
= |
_
u
m
dr|
2
(3.21)
gives the probability of operator

A having the eigenvalue a
m
, when the
system is described by a state . To see this we note that the average value
of the operator

A in state is given
a =
_

Adr
=
n
C
m
C
n
_
u
m

Au
n
dr
=
n
C
m
C
n
a
n
_
u
m
u
n
dr
=
n
C
m
C
n
a
n
mn
=
m
|C
m
|
2
a
m
, (3.22)
The weighing factor |C
m
|
2
above gives the probability of nding the Eigen-
value a
m
.
(e) The operators do not necessarily obey a commutative law, i.e. two
operators

Aand

B need not give

A
B =

B

A. If

A
B equals

B

A, the operators
are said to commute, i.e.
[

A,

B] =

A
B

B

A = 0 (3.23)
[

A,

B] is called the commutator of two operators.
(f) If two observables commute, then it is possible to nd a set of func-
tions which are simultaneously eigenfunctions of

A and

B. If they do not
commute, i.e. [

A,

B] = 0, this cannot be done except for a state which
has [

A,

B] = 0.
We now show that if u
n
is a simultaneous eigenfunction of

A and

B
corresponding to eigenvalues a
n
and b
n
, then
[

A,

B]u
n
= 0 . (3.24)
Now
Au
n
= a
n
u
n
, (3.25a)
Bu
n
= b
n
u
n
. (3.25b)
Further
Bu
n
=

Ab
n
u
n
= b
n

Au
n
= b
n
a
n
u
n
, (3.26a)
B

Au
n
=

Ba
n
u
n
= a
n

Bu
n
= a
n
b
n
u
n
. (3.26b)
Therefore
(

A
B

B

A)u
n
= (b
n
a
n
a
n
b
n
)u
n
= 0 ,
i.e.
[

A,

B]u
n
= 0 . (3.27)
The implication of this result is as follows:
Since u
n
form a complete set so that an arbitrary function can be
expanded in terms of them, it follows that
[

A,

B] = 0 .
Since is arbitrary, [

A,

B] = 0. Thus if a set of simultaneous eigenfunctions
of two observables

A and

B exist, then

A and

B commute.
If [

A,

B] = 0 and [

A,

C] = 0 but [

B,

C] = 0, then it is not possible to nd
functions which are simultaneously eigenfunctions of

A,

B and

C. It is only
possible to nd eigenfunctions for

A and

B or for

A and

C. Corresponding
to this, we can only make simultaneous measurements of the observables
corresponding to the pair of operators

A and

B or to the pair

A and

C, it
is not possible to measure

B,

C together.
3.3 Continuous Spectrum and Dirac Delta Functions
(a) Continuous Spectrum
So far we have considered the case when the eigenvalues of an operator
A are discrete. In case eigenvalues of an operator take on continuous values,

the sum in the completeness relation (3.19) takes the form of an integral
(x) =
_
C(a)u
a
(x)da , (3.28)
where the label a corresponds to continuous set of eigenvalues and replaces
the discrete label n in Eq. (3.19). For simplicity we rst consider to be a
function of a single variable x only; the generalisation to three dimensions
is straightforward.
Now using (3.28)
_
u
a
(x)(x)dx (u
a
|)
=
_
daC(a)(u
a
|u
a
) , (3.29)
where a
lies in the domain of integration of a. Now the orthogonality

condition (3.18) becomes
_
u
a
(x)u
a
(x)dx (u
a
|u
a
)
= 0 when a = a
. (3.30)
For a = a
, it does not have to vanish. In fact it must be innitely large

at a = a
because if it is nite at a = a
, then the integral on right-hand

side of Eq. (3.29) vanishes but (x) does not vanish in general. But this
innity must be such that
_
u
a
(x)(x)dx = C(a
)
_
da(u
a
|u
a
) , (3.31)
so that in analogy with Eq. (3.20), we have
C(a
) =
_
u
a
(x)(x)dx (3.32)
with
_
da(u
a
|u
a
) = 1 . (3.33)
Thus (u
a
|u
a
) has the peculiar property: it is zero everywhere except at
a = a
[see Fig. 3.1] and at a = a
it is innitely large such that its integral

is 1.
(aa
)
a
g
1
g
2
a
Fig. 3.1 The Dirac delta function.
Such a function is called Dirac -function and is written as
(a a
) = 0 for a = a
= for a = a
(3.34a)
such that
_
da(a a
) = 1 . (3.34b)
Thus we write
(u
a
|u
a
) =
_
u
a
(x)u
a
(x)dx
= (a a
) , (3.35)
corresponding to orthonormality relation (3.17) for discrete set. Substitut-
ing Eq. (3.38) into Eq. (3.29), we have
_
u
a
(x)(x)dx =
_
daC(a)(a a
) .
Comparing it with Eq. (3.35), we have
_
daC(a)(a a
) = C(a
) . (3.36)
This is the fundamental property of the -function which we require.
The generalisation to three dimensions is obvious
x r, a a, a
.
Thus Eqs. (3.28), (3.32), (3.34), (3.35) and (3.36) respectively become
(r) =
_
C(a)u
a
(r)da (3.37)
C(a
) =
_
u
a
(r)(r)dr (3.38)
_
(a a
) = 0 for a = a
,
= for a = a
.
(3.39a)
_
da(a a
) = 1 , (3.39b)
(u
a
|u
a
) = (a a
) , (3.40)
_
C(a)(a a
)da = C(a
) . (3.41)
Here
(a a
) = (a
x
a
x
)(a
y
a
y
)(a
z
a
z
) . (3.42)
(b) Closure Relations We have
(r) =
n
C
n
u
n
(r) (for discrete set) (3.43a)
=
_
C(a)u
a
(r)da (for continuous set) . (3.43b)
Then
C
n
=
_
u
n
(r
)(r
)dr
, (3.44a)
C(a) =
_
u
a
(r
)(r
)dr
. (3.44b)
Substituting in Eq. (3.43a), we have for discrete set
(r) =
n
_
_
u
n
(r
)(r
)dr
_
u
n
(r)
=
_
_
n
u
n
(r)u
n
(r
)
_
(r
)dr
.
Thus it follows that
n
u
n
(r)u
n
(r
) = (r r
) . (3.45a)
The corresponding relation for continuous set is
_
u
a
(r)u
a
(r
)da = (r r
) . (3.45b)
These are known as Closure Relations. These are equivalent to complete-
ness relations, since one can write (e.g. discrete set)
(r) =
_
(r
)(r r
)dr
=
_
(r
n
u
n
(r)u
n
(r
)dr
=
n
_
_
u
n
(r
)(r
)dr
_
u
n
(r)
=
n
C
n
u
n
(r) . (3.46)
(c) A Simple Representation of -function Consider the function
_
e
ia(xx
)
da .
Now e
ia(xx
)
is an oscillating function and the above integral is not dened.
It is a question of agreeing to give a value to this integral. The prescription
is
_

e
ia(xx
)
da = lim
0
_
_
0
e
ia(xx
)+a
da +
_

0
e
ia(xx
)a
da
_
= lim
0
_
1
i(x x
) +

1
i(x x
)
_
= lim
0
_
2
2
+ (x x
)
2
_
.
If x = x
, (xx
)
2
is a xed number, no matter how small it may be. Now
when 0,
2
can be neglected in comparison with (x x
)
2
so that the
limit = 0. If x = x
lim
0
_
2
2
+ (x x
)
2
_
= lim
0
2
= .
The behaviour is that of a -function, but we have to verify that its integral
is 1. Thus we calculate
_

_
_

e
ia(xx
)
da
_
dx = lim
0
_

2
+ (x x
)
2
dx
= lim
0
_

2
+
2
d, = (x x
)
= lim
0
_
2 tan
1

= 2 lim
0
_
2

_

2
_
_
= 2 .
Thus
1
2
_

e
ia(xx
)
da = (x x
) . (3.47a)
Its generalisation to three dimension is
1
(2)
3
_
e
ia(rr
)
da = (r r
) . (3.47b)
(d) Properties of -function
f(x)(x b) = f(b)(x b) ,
x(x) = 0 ,
(x) = (x) ,
(bx) =
1
|b|
(x) ,
(x
2
b
2
) =
1
2b
_
(x b) +(x +b)
_
, b > 0
_
(a x)dx(x b) = (a b) .
These equations have meaning only in the sense of integration; for example,
the rst one means
_
f(x)(x b)dx = f(b) .
(bx) =
1
|b|
(x) means
_
(bx)dx =
1
| b |
.
(e) Fourier Transform
The completeness relation, in terms of eigenfunctions
1
2
e
iax
becomes
f(x) =
1
2
_

C(a)e
iax
da , (3.48)
1
2
_

f(x)e
ia
x
dx =
1
(2)
_

daC(a)
_

e
ix(aa
)
dx
=
_
daC(a)(a a
)
= C(a
) .
Therefore
C(a) =
1
2
_

f(x)e
iax
dx . (3.49)
C(a) and f(x) are called the Fourier transforms of each other.
The generalisation to three dimensions is
f(r) =
1
(2)
3/2
_
C(a)e
iar
da , (3.50a)
C(a) =
1
(2)
3/2
_
f(r)e
iar
dr . (3.50b)
(f) Momentum Eigenfunctions (An Example of Continuous
Spectrum of Eigenvalues
The momentum operator in Schrodinger representation is
p = i

x
.
Eigenvalue equation is
pu
p
(x) = pu
p
(x) ,
i

x
u
p
(x) = pu
p
(x) . (3.51)
A solution of this equation is
u
p
(x) = Bexp
_
i
px
_
. (3.52)
Here eigenvalue p is a continuous variable and takes on any value. Above
we have taken the momentum in x direction. For three dimensions
p = i
and
pu
p
(r) = pu
p
(r) ,
u
p
(r) = Bexp
_
i
p r
_
. (3.53)
Now
(u
p
|u
p
) =
_
u
p
(r)u
p
(r)dr
= |B|
2
_
e
(i/)(pp
)r
dr
= |B|
2
3
(2)
3
(p p
) .
Thus if we select
B =
1
(2)
3/2
,
then
(u
p
|u
p
) = (p p
) . (3.54)
Thus normalised momentum eigenfunctions are
u
p
(r) =
1
(2)
3/2
e
(i/)pr
. (3.55)
Since these eigenfunctions form a complete set we can write
(r) =
1
(2)
3/2
_
C(p)e
(i/)pr
dp , (3.56a)
where
C(p) =
1
(2)
3/2
_
e
(i/)pr
(r)dr (3.56b)
(r) and C(p) are the Fourier transform of each other.
Now average value of the momentum operator is given by
p = p =
_

(r) p(r)dr
=
1
(2)
3
dp
dpC
(p
)C(p)e
(i/)p
r
(i)e
(i/)pr
dr
=
1
(2)
3
dp
dpC
(p
)C(p)
pe
(i/)(pp
)r
dr
=
dp
dpC
(p
)C(p)p(p p
)
=
_
|C(p)|
2
pdp . (3.57)
Thus |C(p)|
2
is the probability of momentum operator p having eigen-
value p when the system is in state (r). In other words, in a measurement
of the momentum of a particle, the probability of nding the result p is
|C(p)|
2
. Thus C(p) may be regarded as the wave function, in momen-
tum space just as (r) is the wave function in r space. C(p) is sometimes
written as (p).
3.4 Uncertainty Principle and Non-Commutativity of
Observables
In quantum mechanics, two observables

A and

B do not necessarily com-
mute and obey a commutative law, i.e. in general
[

A,

B] = 0 . (3.58)
This statement is essentially equivalent to the uncertainty principle which
expresses the limitations on our knowledge imposed by mutual disturbances
of observations. Eq. (3.58) implies that it is not possible to nd simultane-
ous eigenfunctions of

A and

B i.e. we cannot have an exact knowledge of
the result of measurement of

A and

B simultaneously.
We now show explicitly that Eq. (3.58) leads to the uncertainty prin-
ciple.

A and

B being observables are hermitian. Let a and

b denote the
average values of large number of measurements of

A and

B respectively.
Dene
A a =

A ,
b =

B . (3.59)
It is clear from Eq. (3.59) that and are hermitian operators so that we
have
=
2
,
=
2
.
The mean square deviations of the measured values, of

A and

B about the
mean are given by
(a)
2
= (

A a)
2
=
2
,
(b)
2
= (

B b)
2
=
2
. (3.60)
Now
(a)
2

2
=
_

(x)(x)dx
=
_
(
dx
=
_
()
dx
=
_
||
2
dx .
Then
2
=
_
_
||
2
dx
__
_
||
2
dx
_
_
()
dx
2
. (3.61)
This follows from the Schwartz inequality
_
_
| f |
2
dx
__
_
| g |
2
dx
_
_
f
gdx
2
.
Hence
(a)
2
(b)
2
_
()
dx
2
=
_
(
dx
2
=
dx
2
=
+
2
dx +
_

2
dx
2
=
P iQ
2
, (3.62)
where
P =
_

+
2
dx ,
Q =
_

i

2
dx .
Since
+
2
and i
2
are hermitian operators and the average value of
a large number of measurements of a hermitian operator is real, therefore
P and Q are real numbers.
Thus Eq. (3.62) gives
(a)
2
(b)
2
P
2
+Q
2
Q
2
=
i

2
dx
2
=
B

B

A
2
dx
2
, (3.63)
since from Eq. (3.59) =

A
B

B

A.
In particular if

A = p,

B = x, [ p, x] = i
(a)
2
= (p)
2
,
(a)
2
= (x)
2
,
(p)
2
(x)
2

2
4
|
_

dx|
2
=

2
4
.
The root mean square deviation is often called the uncertainty (standard
deviation), i.e.
p =
_
(p)
2
, x =
_
(x)
2
. (3.64)
Hence
px /2 , (3.65)
where p and x denote the uncertainties in the measured values of p
and x. If
[

A,

B] = 0
there is no mutual disturbance, and the result of simultaneous measure-
ments of observables

A and

B can be known exactly.
Example
Momentum and energy operators for a free particle are given by
A = p i

x
B = H =
p
2
2m

2
2m
2
x
2
(3.66)
so that
_
p, H
(x) =
_
i

x

2
2m
2
x
2
_
(x)
= 0
which is true for an arbitrary function (x). Thus
[ p, H] = 0 .
The energy and momentum of a free particle can be known exactly, simul-
taneously. In other words, it is possible to nd a wave function which is a
simultaneous eigenfunction of both momentum and energy.
3.5 Problems
3.1 If
A denotes the average value for a large number of measurements

of an operator

A for an arbitrary state function , show that A
is real if

A is hermitian.
3.2 The state function for a free particle moving in x-direction is given
by
(x) = Ne
(x
2
/2
2
+ip
0
x/)
.
Normalise this wave function. Find the state function (p) in mo-
mentum space.
(i) Show that for the state (x) given above
x = 0 ,
p = p
0
,
x
2
=

2
2
,
p
2
= p
2
0
+
1
2
2
.
Hence show that
(x)
2
= (x x)
2
=

2
2
(p)
2
= (p p)
2
=
1
2
2
so that
xp =
1
2
.
(ii) Using the relations
p =
_
p|(p)|
2
dp
p
2
=
_
p
2
|(p)|
2
dp
show that
p = p
0
,
p
2
= p
2
0
+
1
2
2
.
_
Useful integral
_
+
x
2n
e
x
2
dx =
1
n+
1
2
(2n)!
2
2n
n!
_
3.3 Show that for a particle of mass m, moving in a potential V (r),
[H, r] = i
p
m
,
[ p, H] = [ p, V (r)] = iV .
Using the above results and the fact that H is hermitian, show that
m
d
dt
r = p ,
d
dt
p = V .
(Note that Newtons law is valid for expectation values.)
3.4 Using the result
[H, x] = i
p
m
,
for a particle of mass m moving in x-direction in a potential V (x),
show that the average value of its momentum in a stationary state
with discrete energy is zero.
3.5 A particle is in a state
(x) =
1
a
sin
_
5x
a
_
, |x| a
= 0 elsewhere ,
show that the probability for the particle to be found with momen-
tum p is given by
100a
2
sin
2
(pa/)
(p
2
a
2
/
2
25
2
)
.
3.6 A particle of mass m is conned by an innite square well potential
V (x) = 0, |x| a; V (x) = , |x| > a. If the particle is in the state
(x) = x, |x| a ,
(x) = 0 , |x| > a ,
nd the probability that a measurement of energy will give the
result
E
n
=

2
2m
_

2
4a
2
_
n
2
.
3.7 For a free particle, nd a wave funcion which is a simultaneous
eigenfunction of both momentum and energy. This is not so for a
particle moving in a potential since then | p, H| = 0 [cf. Problem
3.3].
3.8 a) If a particle is in a state
(x) =
_
2
2
_1
4
e
x
2
2
nd the probability of nding it in the momentum eigenstate
u
p
(x) =
_
1
2
e
px
.
b) If it is in a state
u
p
(x) =
_
2
sin nx, 0 x
show that the probability of nding it with momentum p is given
by
|(p)|
2
=
1
sin
4
_
(
p
n)
2
_
_
p
n
2
_
2
.

Basic Postulates of Quantum Mechanics

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Basic Postulates of Quantum Mechanics

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September 20, 2012 15:38 BC 8534 - 9in x 6in Quantum Mechanics 2nd Edition

dr = 1, and there exist suitable boundary conditions.

A are discrete. In case eigenvalues of an operator take on continuous values,

lies in the domain of integration of a. Now the orthogonality

, it does not have to vanish. In fact it must be innitely large

, then the integral on right-hand

[see Fig. 3.1] and at a = a

it is innitely large such that its integral

A denotes the average value for a large number of measurements

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