Physical Chemistry 2

nd
Edition
Thomas Engel, Philip Reid
Chapter 14
The Quantum Mechanical Postulates
2010 Pearson Education South Asia Pte Ltd
Physical Chemistry 2
nd
Edition
Chapter 14: The Quantum Mechanical Postulates
Objectives
Introduce 5 postulates which relate to
quantum mechanics.
2010 Pearson Education South Asia Pte Ltd
Physical Chemistry 2
nd
Edition
Chapter 14: The Quantum Mechanical Postulates
Outline
1. The Physical Meaning Associated with the
Wave Function
2. Every Observable Has a Corresponding
Operator
3. The Result of an Individual Measurement
4. The Expectation Value
5. The Evolution in Time of a Quantum
Mechanical System
2010 Pearson Education South Asia Pte Ltd
Physical Chemistry 2
nd
Edition
Chapter 14: The Quantum Mechanical Postulates
14.1 The Physical Meaning Associated with the Wave
Function
Postulate 1
The state of a quantum mechanical system
is completely specified by a wave function


The probability that a particle will be found
at time t
0
in a spatial interval of width dx
centered at x
0
is given by

( ) t x,
( ) ( )dx t x t x
0 0 0 0
, ,
2010 Pearson Education South Asia Pte Ltd
Physical Chemistry 2
nd
Edition
Chapter 14: The Quantum Mechanical Postulates
14.1 The Physical Meaning Associated with the Wave
Function
For sound wave, the wave function is
associated with the pressure at a time t and
position x.
For a water wave, is the height of the
wave
( ) t x, +
( ) t x, +
2010 Pearson Education South Asia Pte Ltd
Physical Chemistry 2
nd
Edition
Chapter 14: The Quantum Mechanical Postulates
14.1 The Physical Meaning Associated with the Wave
Function
The normalization condition for a particle
confined in a 1-D space of infinite extent is



(x,t) must satisfy several mathematical
conditions:
1. Wave function must be a single-valued function
2. The first derivative must be continuous function
3. Wave function cannot infinite amplitude over a finite
interval
( ) ( ) 1 , , * = + +
}

dx t x t x
2010 Pearson Education South Asia Pte Ltd
Physical Chemistry 2
nd
Edition
Chapter 14: The Quantum Mechanical Postulates
14.2 Every Observable Has a Corresponding
Operator
Postulate 2
For every measurable property of the system in
classical mechanics such as position, momentum, and
energy, there exists a corresponding operator in
quantum mechanics. An experiment in the laboratory
to measure a value for such an observable is
simulated in the theory by operating on the wave
function of the system with the corresponding
operator.

2010 Pearson Education South Asia Pte Ltd
Physical Chemistry 2
nd
Edition
Chapter 14: The Quantum Mechanical Postulates
14.2 Every Observable Has a Corresponding
Operator
All quantum mechanical operators belong to a
mathematical class called Hermitian
operators that have real eigenvalues.
2010 Pearson Education South Asia Pte Ltd
Physical Chemistry 2
nd
Edition
Chapter 14: The Quantum Mechanical Postulates
14.3 The Result of an Individual
Measurement
Postulate 3
In any single measurement of the observable that
corresponds to the operator , the only values
that will ever be measured are the eigenvalues of
that operator.

A

2010 Pearson Education South Asia Pte Ltd

Physical Chemistry 2
nd
Edition
Chapter 14: The Quantum Mechanical Postulates
14.3 The Result of an Individual
Measurement
The measured energy values of an atom are the
eigenvalues of the time-independent
Schrdinger equation:

( ) ( ) t x E t x H
n n n
, ,

+ = +
2010 Pearson Education South Asia Pte Ltd
Physical Chemistry 2
nd
Edition
Chapter 14: The Quantum Mechanical Postulates
14.4 The Expectation Value
Postulate 4
If the system is in a state described by the wave
function , and the value of the observable
a is measured once each on many identically
prepared systems, the average value (also called
the expectation value) of all of these
measurements is given by


( ) t x,
( ) ( )
( ) ( )
}
}

=
dx t x t x
dx t x A t x
a
, , *
,

, *


2010 Pearson Education South Asia Pte Ltd
Physical Chemistry 2
nd
Edition
Chapter 14: The Quantum Mechanical Postulates
14.4 The Expectation Value
As eigenfunctions form an orthonormal
set, it is normalized.
Thus

m
m
m m m
m
m
a b b b a a


=

=
= =
1
2
*
1
A

2010 Pearson Education South Asia Pte Ltd

Physical Chemistry 2
nd
Edition
Chapter 14: The Quantum Mechanical Postulates
14.5 The Evolution in Time of a Quantum
Mechanical System
Postulate 5
The evolution in time of a quantum mechanical
system is governed by the time-dependent
Schrdinger equation:

( )
( )
t
t x
ih x,t H
c
c
=
,

2010 Pearson Education South Asia Pte Ltd

Physical Chemistry 2
nd
Edition
Chapter 14: The Quantum Mechanical Postulates
14.5 The Evolution in Time of a Quantum
Mechanical System
We call this behavior deterministic in contrast
to the probabilistic nature of Postulate 4.
When time at t
0
, Postulate 4 applies.
When t
1
> t
0
, without carrying out a
measurement in this time interval, Postulate
5 applies.
If at time t
1
, we carry out a measurement
again, Postulate 4 will apply.