PHYSICAL CHEMISTRY (1)

CHAPTER 3
Quantum Mechanical Postulates

Tae Kyu Kim

Department of Chemistry
Rm. 445 (tkkim@yonsei.ac.kr)
http://learnus.org

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SUMMARY (CHAPTER 1)

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 Quantum Mechanical Postulates
There is no deviation of quantum mechanics from some other theory. Instead
quantum mechanics is based on several assumptions, which we call postulates.
Chapter 2 presents these postulates, thus giving us the formal theory that
underlies quantum mechanics. But it should be noted that the only justification
for the postulates is that they lead to predictions about the properties of atoms
and molecules and about spectroscopy, kinetics, and other physical phenomena
that are in accord with experiment. There have been many tests of quantum
mechanics over the years – many with extraordinary precision – and at the point
there is no indication of error in any predictions. Thus we can truly say that
quantum mechanics works.

NEW THEORY FOR DESCRIBING NATURE

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 Synopsis
The main ideas are (for quantum mechanics postulates):
− The behavior of electrons by now known to have wavelike properties, can be
described by a mathematical expression called a wavefunction.

− The wavefuncion contains within it all possible information that can be known
about a system. Wavefunctions are not arbitrary mathematical functions, but must
satisfy certain simple conditions, such as continuous. The most important condition is
that the wavefunction must satisfy time-dependent Schrödinger equation. With
certain assumptions, time can be separated from the wavefunction, and what
remains is a time-independent Schrödinger equation which we mainly focus.

− In the application of these conditions to real system, wavefunctions are found that
do indeed yield information that agrees with experimental observations of these
systems: quantum mechanics predicts values that agree with experimentally
determined measurements. The simplest real system to understand is the hydrogen
atom, a system that Rydberg, Balmer, and Bohr had studied with different degrees of
success. To the extent that quantum mechanics not only reproduces their success but
also it, quantum mechanics is superior to their to their theory trying to describe the
behavior of subatomic particles.

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 Postulates of Quantum Mechanics
(POSTULATE I) Wavefunction (Ψ) is a well-behaved, square
integrable function and has all the information of a system.
(POSTULATE II) |Ψ|2 is the probability of finding the particle.
(POSTULATE III) For every observable property, there is a
corresponding linear Hermitian operator.
(POSTULATE III’) Ψ can be obtained by solving time-dependent (or
independent) Schrödinger equation:
2 2
∂  d
i Ψ = Hˆ Ψ , − ( Ψ + v( x) ) = E Ψ
∂t 2m dx 2

(POSTULATE IV) If Aˆψ a = aψ a for a system Ψa, we always get a as a

results of measurements.
(POSTULATE V) The average(expectation) value of an observable A
is given by ∫ Âψ dτ
ψ *

A =
∫ ψ dτ
ψ *

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Definition of Wavefunctions

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 Definition of Ψ and |Ψ|2 – P1&2 (1)
• We shall take the de Broglie relation as our starting point and the abandon
the classical concept of particle moving along the trajectories.

• We adopt the quantum mechanical

view that a particle is spread through
space like a wave

• To describe the distribution, we

introduce the concept of wavefunction
(Ψ), in place of trajectory. It is modern
term for de Broglie’s matter wave

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 Definition of Ψ and |Ψ|2 – P1&2 (2)
• The state of a system can be described by an expression called a
“wavefunction”. Wavefunction contains all information of a system.

• For various physical and mathematical

reasons, these Ψ’s are limited and
constrained, to being functions that are:

Single valued
Continuous
Square integrable

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 Definition of Ψ and |Ψ|2 – P1&2 (3)
• How can we discuss the motion of electrons in any detail at all?
• Because of the uncertainty principle, Born suggested that we are not think of
Ψ as indicating a specific path of an electron. It is very difficult to establish
absolutely that a particular electron is in a particular position and time. Rather
over a long period of time, the electron has a certain probability of being in
certain region.
b

∫ Ψdτ
*
P= Ψ
a

2
• Ψ ( x1 , y1 , z1 , x2 , y2 , z2 , t ) dτ is the probability of finding particle 1 between the
points ( x1 , y1 , z1 ) and ( x1 + dx1 , y1 + dy1 , z1 + dz1 ) , particle 2 between the points
( x2 , y2 , z2 ) and ( x2 + dx2 , y2 + dy2 , z2 + dz2 ) at time t. If the particles are
indistinguishable, then the probability density refers to any particular rather
than a specific particle.
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 Normalization
• The Born interpretation suggests that there should be another requirement
for acceptable wavefunctions. If the probability for a particle having
wavefunction were evaluated over the entire space in which the particle exists,
then the probability should be equal to 1 or 100 %. In order for this to be the
case, wavefunctions are expected to be normalized.

∫
−∞
Ψ * Ψdτ =1

• Example: Ψ ( x) =
sin (π x / 2 ) where x is the only variable from x = 0 to x = 1.

Ψ → NΨ
1 1 *
 πx  πx
∫ ( N Ψ ) N Ψdx
*
∫0
*
= N = N  sin   sin  dx 1
0  2   2 
∴ N =2
πx
Ψ ( x) =2 sin
2
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 Spherical Coordinate (r, θ, φ)
• The three-dimensional system of most importance to us is the atom. Closed-
shell atoms are spherically symmetric, so that we might expect atomic wave
functions to be best described by spherical coordinate.
Cartesian coordinate (x, y, z) → Spherical coordinate (r, θ, φ)

x = r sin θ cos φ
y = r sin θ sin φ
z = r cos θ
0 ≤ r ≤ ∞, 0 ≤ θ ≤ π , 0 ≤ φ ≤ 2π

dV = dxdydz
= ( r sin θ dφ )( rdθ )( dr )
= ( r 2 sin θ dφ ( rdθ ) dr )

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 Example: Normalization in Spherical Coordinate
• Normalize the function e − r over the interval 0 ≤ r ≤ ∞, 0 ≤ θ ≤ π , 0 ≤ φ ≤ 2π .

2π π ∞
N2 ∫ ∫∫ Ψ *
Ψ r 2
sin θ drdθ dφ =1
0 0 0
2π π ∞
N2 ∫ ∫ ∫ r sin θ drdθ dφ = 1
e −2 r 2

0 0 0
∞
 ∞

N ∫ r e dr 1=
4π=2 2 −2 r
 ∫ x e dx n !/ a 
n − ax n +1

0 0 
2! 1 1
4π N 3= 1 ∴ N=
2
→ Ψ= e− r
2 π π

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Extracting Information
from the Wavefunction

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 Observable & Operator – P3 & P4 (1)
• When studying the state of system, one typically makes various
measurements of its properties, such as mass, volume, position, momentum,
and energy. Each individual property is called an observable.

• Since quantum mechanics postulate that the state of a system is given by a

wavefunction, how does one determine the value of various observables
(position or momentum or energy) from a wavefunction?

• To determine the value of an observable, you have to perform some

mathematical operation on a wavefunction which is represented by operator.

d
2×3 =6
Performance of an dx
( 3x3 + 4 x 2 + 5) = 9 x 2 + 8 x
operation typically
yields some
expression either a
Mˆ ( 2,3) = 6 number or a function Dˆ ( 3 x 3 + 4 x 2 + 5 ) = 9 x 2 + 8 x

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 Observable & Operator – P3 & P4 (2)
• When an operator acts on a function, some other function is usually
generated. There is special type of operator/function combination that, when
evaluated, produces some constant or group of constants times the original
function.

Eigenfunction-Eigenvalue Equation

d2
2 (
sin 4 x ) = −16 ( sin 4 x )
dx
B̂Ψ = K Ψ

• Another postulate: For every physical observable of interest, there is a

corresponding operator. The only values of the observable that will be
obtained in a single measurement must be eigenvalues of the eigenvalue
equation constructed from the operator and wavefunction. (P3 and P4)

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 Observable & Operator – P3 & P4 (3)
• Two basic observables are position & the corresponding linear momentum.
Many other observables are various combinations of these two basic
observables.
x̂ → x
∂
pˆ x → − i
∂x

• The postulates regarding eigenfunctions and eigenvalue equations get more

specific: the only values of the observables are those that are eigenvalues of
the wavefunction when operated upon by the corresponding operator. No
other values will be observed. In addition, not all experimental quantities are
determined by any given wavefunction. Rather a given wavefunction is an
eigenfunction of some operator, but not an eigenfunction of other operators.

• Example: What is the value of the momentum observable for Ψ =e − i 4 x ?

∂ −i 4 x
−i=
∂x
( e ) 4=
i 2  ( e − i 4 x ) −4 ( e − i 4 x )
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Postulate 3
For every observable property, there is a linear Hamiltonian operator that is
obtained by expressing the classical form in Cartesian coordinate x and linear
momentum px and making replacements x̂ → x and pˆ x → −i ( ∂ / ∂x )

Postulate 4
If Ψa is an eigenfunction of the operator  with eigenvalue a, then if we
measure the property A for a system whose wavefunction is Ψa, we always
get a as the results.

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 Operator – 1
• Postulate 2: For every observable property, there is a linear
Hermitian operator that is obtained by expressing x and px.

− A linear operator: Bˆ (φ + cψ ) =Bˆφ + cBˆψ

*
 
− A Hermitian operator: ∫
* ˆ
φ Bψ dτ =  ∫ ψ Bφdτ  * ˆ

all space  all space 

− An important property of Hermitian operator:

*
 
( )
*
ˆ * ˆ
∫ ψ Bψ dτ ==  ∫ ψ Bψ dτ  = a real number
all space  all space 

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 Operator – 2
• Is px Hermitian?
*
* ˆ

 * ˆ

  ∂ ∂
∫ φ B ψ dτ =  ∫ ψ B φ dτ  pˆ x = = −i
all space  all space
 
 i ∂x ∂x

dg df
∫f dx
= fg − ∫ g dx
dx
dx

 ∂  * ∂ψ ∞ ∂φ *
∫  ∂x 
φ *
 −i  ψ dx =−i  ∫ ∂x
φ dx =−i φ *
ψ − ( −i ) ∫ψ dx
−∞ ∂x
*
∂φ * * ∂φ
*
 ∂  *
i ∫ψ
= ∫
dx =ψ ( )
− i  dx ∫
=ψ  − i   φ dx
∂x ∂x  ∂x 
*
  ∂  
=  ∫ψ *  −i  φdx 
  ∂x  

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 Other Properties of Operators
• Operator multiplication is associative and dissociative.

ABC (
ˆ ˆ ˆ [ f ( x) ] = Aˆ Bˆ Cf

ˆ ( x) 
 )
• Operator multiplication is not necessarily commutative.

ˆ ˆ [ f ( x) ] = BA
AB ˆ ˆ [ f ( x) ] : commutative

 ∂  ∂
• Commutator:  Aˆ , Bˆ  ≡ AB
ˆ ˆ − BA
ˆˆ [ x] 
x , p = x , −i   (
= −i  )  x, 
   ∂x   ∂x 
 ∂ ∂ 
=( −i )  x − x  =( −i )( −1) =i ≠ 0
 ∂x ∂x 

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 Other QM Operators
• Operator can be generated by combination of x and px. x → x

V=
1 2
x → Vˆ =
1 2
x  ∂
2 2 px →
i ∂x
1 2 ˆ 1   ∂   ∂    2
∂ 2

E=
k p → E
=    = −  2 
2m 2m  i ∂x  i ∂x   2 m ∂x 

pˆ x 2 + pˆ y 2 + pˆ z 2 2  ∂ 2 ∂2 ∂2  2 2
→ −  + +  =− ∇
2m 2m  ∂x 2 ∂y 2 ∂z 2  2m
2

Hˆ =Eˆ k + Vˆ =− ∇ 2 + V ( x, y, z ) : Hamiltonian Operator
2m
2
2 n ∇ j
→− ∑ + V for n interacting particles
2 j =1 m j

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 Other Operators in QM

l= r × p

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 P4 & Uncertainty Principle
• Postulate 4: If Ψa is an eigenfunction of the operator  with eigenvalue a, then if
we measure the property A for a system whose wavefunction is Ψa, we always get
a as the results.
∂
• Let say: pˆ x=
ψ l plψ l → − i =ψ l plψ l
∂x
∂ ∂ψ l dψ l
−i
∂x
ψ l = plψ l → − i
ψl
= pl ∂x → ∫ −i ψl
= pl ∫ dx

→ − i lnψ l =pl x
Aeipl x / 
∴ψ l =

2
These momentum eigenfunctions are called plane
ψl = A A *
waves, and they have the property that probability
function is a constant, independent of x. This means
that the coordinate x is completely undetermined:
Heisenberg Uncertainty Principle

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 The Schrödinger Equation (P3’)
• One of the most important ideas in QM is the Schrödinger Eq.
which deals with the most important observable: energy

ˆ ˆ ˆ   2
∂ 2
 ˆ
H=Ek + V =− 2 
+ V ( x)
 2 m ∂x 
 2 ∂ 2 ˆ ( x)  Ψ = E Ψ : Time-independent
→ − 2
+ V 
 2 m ∂x  Schrödinger Equation
• Example: Consider an electron confined to some fine system. The state of electron is
described by the wavefunction
= Ψ =2 sin kπ x (k const ) . Assume that the potential
energy is zero. What is the energy of the electron?

 2 ∂ 2  2  2 k 2π 2
 −
 2m ∂x
2
+ 0 

2 sin k π x =−
2m
( − k π )
2 2
( )
2 sin kπ x → E =
2m

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 Time Independent Schrödinger Equation – P3’
∂
• Ψ(x,t) is obtained by solving: i Ψ= Hˆ Ψ : Time-dependent
∂t Schrödinger Equation
∂H
If , = 0 → Ψ ( x, t ) = ψ ( x) f (t ) : Separation of variable
∂t

1 df (t ) Hψ ( x)
i = = constant = E
f (t ) dt ψ ( x)
Ĥ Ψ = E Ψ
f (t ) = e − iEt / 
2 2
Ψ ( x, t ) =
ψ ( x ) : Independent of time
e − iEt / ψ ( x)
Ψ ( x, t ) = (stationary state)

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Postulate 3
For every observable property, there is a linear Hamiltonian operator that is
obtained by expressing the classical form in Cartesian coordinate x and linear
momentum px and making replacements x̂ → x and pˆ x → −i ( ∂ / ∂x )

Postulate 4
If Ψa is an eigenfunction of the operator  with eigenvalue a, then if we
measure the property A for a system whose wavefunction is Ψa, we always
get a as the results.

Postulate 3’
∂
Ψ(x,t) is obtained by solving: i Ψ= Hˆ Ψ which is known as
∂t
the time-dependent Schrödinger equation

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Predicting Outcomes of
the Experiments

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 Expectation Value – P5
• Postulate 4 tell us we will measure when we consider eigenfunctions
associated with a dynamical variable of interest. In the more general case where
the wavefunctions are not eigenfunctions of the desirable operator, we must
calculate the average (or expectation) value.

∫ Âψ dτ
ψ *

A =
∫ ψ dτ
ψ *

• If Ψ is an eigenfunction of operator A (case I), the expectation value is just the

eigenvalue
∫ Âψ dτ
ψ *

∫ ψ ψ τ ∫ ψ dτ a
ψ
* *
< A>
= = = a d a=
∫ ψ dτ
ψ *

• If Ψ is NOT an eigenfunction of operator A (case II), what we can expect?

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 Expectation Value – P5
• We have to use the completeness of well-behaved func. – It is possible to
expand any well-behaved func. exactly in terms of the complete set of
eigenfunctions of Ĥψ = Eψ . [Section 2.7.5]

ψ ( x) = ∑ cnφn ( x)
n
∑=
n
*
cn cn ∑=
n
cn
2
1 ( ∫ψ *
( x= )
)ψ ( x) 1

∞
< a >= ∫ ψ * ( x)Aˆψ ( x)dx
−∞
∞
  
∫−∞ ∑m m m  ∑n n n n  dx
φ φ
* *
= c ( x ) a c ( x )

∞ ∞ ∞
= ∑∑ cm* an cn ∫ φm* ( x)φn ( x)dx
−∞
m n
∞ ∞

∑= ∑c * 2
a c c
m m m m am
m m

weighted average

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 Example – P5
• Free particle in 1D space
 2 d 2ψ k 22
− 2
Eψ
= ψ=
Ae + Be ikx − ikx
E=
2m dx 2m

ψ =Aeikx + Be − ikx =A(cos kx + sin kx) + A(cos kx − sin kx) =2 A cos kx

• What if we measure the momentum for this system?

 d ( 2 A cos kx ) 2k 
pˆψ = =
− sin kx ≠ ( )ψ
i dx i

ψ =cos kx =eikx + e − ikx =ψ → + ψ← Particle (-kħ)

momentum
Particle (kħ)
momentum

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 Postulate 5 & Complete Set
• Complete set of wavefunction:
ψ= c1ψ 1 + c1ψ 1 + ...= ∑c ψ
n
n n

(1) If we measure once, we will get an eigenvalue of corresponding eigenfunction

(2) The probability of getting specific eigenvalue is proportational to the square of
corresponding coefficient
(3) The average value will be the expectation value after infinite number of
measurements

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Postulate 5
The average (or expectation) value of an observable A is given
by:
A =
∫
ψ * Âψ dτ

∫ψ ψ dτ
*

where  is the operator associated with the observable.

Evidently, if Ψ is an eigenfunction of the operator Â, then the
expectation value is just the eigenvalue

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 Properties of the Time-independent
Schrödinger Eigenfunctions – 1
{ }
*
ˆψ dτ ˆφ ) dτ ˆφ )* dτ
• Hermitian operators:
∫ φ ∫ ψ ∫ ψ
* *
= A = ( A ( A

Let Aˆψ = aψ

( )
*
1. If Aˆ is Hermitian, ∫ψ Aˆφ dτ = ∫ φ Aˆψ dτ
*

choose φ = ψ

∫ψ=
a ψ dτ ∫ψ aψ dτ
* * *
→
= ∴ a* a (real)
2. If a is real, Aˆ is Hermitian

Real eigenvalue ↔ Hermitian operator

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 Properties of the Time-independent
Schrödinger Eigenfunctions – 2
• Orthogonality of eigenfunctions:
∫ 1ψ 2 dτ = 0 : orthogonal!
ψ *

=Aˆψ n a=
nψ n Aˆψ m amψ m
∞ ∞

∫ ψ m Aˆψ n dx = an ∫ ψ m ψ n dx 1 m=n
∞

* *

∫−∞ m n
ψ ψ δ δ
*
−∞ −∞ = dx =mn mn 
∞ ∞
 0 m≠n
∫ ψ n Aˆ ψ m dx = am ∫ ψ nψ m dx
* * * *

−∞ −∞

∞ ∞ ∞

∫ ψ m A *
n ∫ n m (
ˆψ dx − ψ Aˆ ψ dx = an − am )
*
∫ ψ n dx =
ψ m
*
*
0 *

−∞ −∞ −∞

∞
When m=n (a
n − am *
) ∫ψ m ψ n dx =
*
0 am*
an =
−∞
∞ ∞
When m≠n (a n − am *
) ∫ψ m ψ n dx = 0
*
∫ψ m ψ n dx = 0
*

−∞ −∞

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Uncertainty Principle

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 Complementarity: Case Study
• Postulate 4: If Ψa is an eigenfunction of the operator  with eigenvalue a, then if
we measure the property A for a system whose wavefunction is Ψa, we always get
a as the results.
∂
• Let say: pˆ x=
ψ l plψ l → − i =ψ l plψ l
∂x
∂ ∂ψ l dψ l
−i
∂x
ψ l = plψ l → − i
ψl
= pl ∂x → ∫ −i ψl
= pl ∫ dx

→ − i lnψ l =pl x
Aeipl x / 
∴ψ l = These momentum eigenfunctions are called plane
2 waves, and they have the property that probability
ψ l = A* A function is a constant, independent of x. This means
that the coordinate x is completely undetermined:
Heisenberg Uncertainty Principle

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 Uncertainty Principle

• It is impossible to specify simultaneously, with arbitrary

precision, both the momentum and the position of a particle.


∆x∆px ≥
2
∆x
= {X 2
− X }
2 1/2

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 Commutation and Complementarity
• Simultaneous eigenfunctions are associated with commuting operators
If  Aˆ , Bˆ  = 0, we can find simultaneous ψ If Gˆψ g=
= ψ and Hˆ ψ hψ
ˆ ˆ ψ = ghψ
GH
“the uncertainty principle holds only ˆ ˆψ = hgψ
HG
for non-commuting operators” (ˆ ˆ − HG
∴ GH )
ˆˆ ψ =
0

∴ Gˆ , Hˆ  =
0
Bˆ  Aˆψ ( x)  
if ψ (x) is an eigenfunction of A
→ an Bˆψ ( x) 
if ψ (x) is an eigenfunction of B
→ anbnψ ( x)

Aˆ  Bˆψ ( x)  
if ψ (x) is an eigenfunction of A and B
→ bn anψ ( x)

• General form of uncertainty principle

1  ˆ ˆ
∆A∆B ≥  A, B 
2

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PC1_CH3 Page. 40
 SUMMARY (Quantum Postulates)
• 입자 계의 상태는 시간과 입자의 좌표인 함수인 파동함수, Ψ로 주어진다. 또한 파동함수는 계
의 상태에 대해서 결정할 수 있는 모든 정보를 내포하고 있다. Ψ는 수학적으로 연속적이고 유
한하며 |Ψ|2은 적분 가능해야 한다.

• 모든 물리적인 관측량 또는 변수 O에 대해서 대응하는 Hermitian 연산자 O가 존재한다. 연산

자는 고전 역학적 식을 위치와 선운동량의 항으로 표현하고 각 x 변수 대신에 x를 곱하고 p 변
수 대신에 ħ/i(∂/∂x)를 그 식에 넣어주어서 만들어진다.

• 일회 측정으로 얻을 수 있는 유일한 관측량의 값은 대응하는 연산자와 파동함수 Ψ로 이루어진

고유값 방정식에서 나타난 고유값이다. 이때 고유값은 반드시 실수이어야한다.

• 파동함수들은 시간-의존 Schrodinger 식을 만족시켜야 한다. (만일 파동함수가 시간의 함수와

위치의 함수로 분리 가능하다고 가정하면 이 식은 시간-무관 Schrodinger 방정식으로 나타낼
수 있다)

• 관측량의 기대값

• 어떤 양자 역학적인 연산자에 대한 일련의 고유 함수들은 수학적인 함수의 완전한 세트이다.

• 주어진 계에 대한 파동함수가 고유값이 an인 파동함수 Ψn의 일차 결합(완전한 세트)로 나타내

면 an이 대응되는 측정값이 될 확률은 |cn|2이다. 그 때 측정을 무한적 시행한다면 관측값의 평
균값은 기대값과 같다.

• 하이젠베르크의 불확정성원리 및 가환연산자

PC1_CH3 Page. 41