A

A A Mamun
Department of Physics
Jahangirnagar University
q Postulates of Quantum Mechanics
v Postulate 1: The state of a quantum mechanical system is completely specified by
a function ψ(r,t), called the wave function or state function. It depends on the
position r of the particle (s) and on the time t, and contains all the information
about the state of the system.

§ What is ψ(r,t)?
o ψ* ψd𝜏 measures the probability that the particle lies in a volume element d𝜏 located at r at
time t.
o ψ(r,t) must satisfy certain mathematical conditions because of this probabilistic
interpretation. The total probability of finding a single particle somewhere is 1, so that we
have the normalization condition:

o ψ(r,t) must be single-valued, finite, square integrateable, differentiable, and continuous. Its
first derivative is also continuous.

Quantum Mechanics/A A Mamun 2

v Postulate 2: To every physical observable 𝓪 in classical mechanics there
$ in quantum mechanics.
corresponds to an operator 𝐀

§ What is a physical observable 𝓪?

A physical observable (𝓪) is defined as any physical quantity, such as position,
momentum, kinetic energy, potential energy, etc. that we use in classical mechanics.
§ What is an operator 𝐀 $?
An operator 𝐀 $ is defined an instruction (viz 𝜕⁄𝜕𝑥 to do something on an object (operand)
or a set of objects (domain of operands) on which the operator 𝐀 $ can meaningfully operate.

§ What are properties of operators?

The algebra of operators results when two or more are combined by addition or
multiplication. The manipulation of operators follow the following elementary rules:
$f1 (x)=f2 (x)
1. Domain of action: A
2. Equality: 𝐴+=B
$ if and only if 𝐴+f(x) = B
$f(x) for every f(x).
$+B
3. Additive: A $=B
$+A
$
$(B
4. Distributive: A $+C
/ ) =A
$B $C
$+ A /
$B
5. Associative: A $𝐶+=(A
$B$)C
/ +A
$(B
$C/)

Quantum Mechanics/A A Mamun 3

6. Operators associated with physical observables:

Physical observable Symbol (𝒶) $)

Operator (A

Position r 𝑟̂
Momentum p ℏ
𝛻
i
Kinetic energy T=P2/2m ℏ2 2
− 𝛻
2m
Potential energy V(r) $
V(r)
E=T+V(r) ℏ?
Total energy $ =−
𝐻 𝛻2 + $
V(r)
?@

Total energy E ℏ 𝜕
𝐸/ = −
i 𝜕𝑡
Angular momentum ℏ
L = r⃗ ×p (𝑟̂ ×𝛻)
H

7. Commutator: The operators 𝐀 $ and 𝐁 $ do not commute in general. The

commutator of operators 𝐀 $ and 𝐁
$ is defined as [𝐀
$, 𝐁
$ ]=𝐀
$. 𝐁
$ −𝐁
$ .L
𝐀 . However,
$, 𝐁
[𝐀 $ ]=0 if they commute.

4
Quantum Mechanics/A A Mamun
Postulate 3-I: The result of the measurement of a physical observable 𝔞 is one of the
eigenvalues of the operator A$ associated with that physical observable This satisfies an
eigenvalue equation: $
AΨ = αΨ

where α is an eigenvalue of the operator 𝐴+ operating on the eigenfunction or eigenstate ΨO.

§ What are eigenvalue equation, eigenvalues and eigenfunctions?

o The equation (containing a parameter), which cannot be solved, in general, for a continues
values of the parameter, but can be solved for some discrete values of the parameter, is
known as eigenvalue equation, and the values of the parameter are known as eigenvalues,
and the solution of this eigenvalue equation is known as eigenfunctions or eigenstates.
o This indicates that postulate 3-I captures the central point of quantum mechanics: The
values of dynamical variables can be quantized.
o The eigenvalues of any operator are real since they are nothing but the measurements of the
physical observable. This means that all operators in quantum mechanics are linear and
Hermitian.

Quantum Mechanics/A A Mamun 5

§ What are linear operators?
$ is said to be linear if and only if 𝐀
§ An operator 𝐀 $[𝚿𝟏 (x)+𝚿𝟐 (x)]=𝐀
$𝚿𝟏 (x)+𝐀
$𝚿𝟐 (x), where

𝚿𝟏 (x) and 𝚿𝟐 (x), are the functions of x. All the operators in quantum mechanics are linear.

§ What are Hermitian operators?

$ is called Hermitian if and only if <𝐇
§ An operator 𝐇 $ 𝚿(x), 𝚿(x)>= <𝚿(x), 𝐇
$ 𝚿(x)>. The

Hermitian operator has real eigenvalue:

$ 𝚿=𝛌𝚿 and 𝐇
§ 𝐇 $ 𝚿 ∗=𝝀∗ 𝚿 ∗ according to the eigenvalue of equation. H
$ is hermitian iff

§ $ 𝚿, 𝚿>=<𝚿,𝐇
<𝐇 $ 𝚿>

§ ⟹ <𝛌𝚿, 𝚿>=< 𝚿, 𝛌𝚿>

§ ⟹ 𝛌 ∫ 𝚿𝚿 ∗ 𝒅𝒙 = 𝝀∗ ∫ 𝚿𝚿 ∗ 𝒅𝒙

§ ⟹ 𝛌 − 𝝀∗ ∫ 𝚿𝚿 ∗ 𝒅𝒙 = 𝟎

§ ⟹ 𝛌 − 𝝀∗ ∫ 𝚿𝚿 ∗ 𝒅𝒙 = 𝟎. 𝐒𝐢𝐧𝐜𝐞 ∫ 𝚿𝚿 ∗ 𝒅𝒙 ≠ 𝟎,
§ 𝛌 = 𝝀∗
§ This indicates that 𝛌 is real, i.e. the Hermitian operator has a real eigenvalue.

Quantum Mechanics/A A Mamun 6

§ Commutator of two operators A and B is usually indicated by [A,B]=(AB-BA). The
commutator bracket obeys the following interesting algebra:
1. [A,B]=-[B,A]
2. [A,A]=0
3. [A,K]=0
4. [A+B,C]=[A,C]+[B,C]
5. [A,(BC)=[A,B]C+B(A,C]

§ Problems: Show that

j
1. [jk , 𝑥]=1

ℏ
2. [Px, 𝑥] = H

?ℏ
3. [x, Pm? F(x)]=− PxF(𝑥)
H

ℏ
4. [x, Px F(x)Px ]= H [F(𝑥)Px + Px F(𝑥)]
?ℏ
5. [x, F(x) Pm? ]=− H
F(𝑥)Px 𝑥

Quantum Mechanics/A A Mamun 7

§ Solutions:
j
1. To show [jk , 𝑥]=1

j j jr
[jk , 𝑥]f = jk 𝑥𝑓 − 𝑥 jk

jr jk jr
= xjk + 𝑓 jk −𝑥 jk
j
= f. So, [jk , 𝑥]=1

ℏ
2. To show [Px, 𝑥] = H

[Px, 𝑥]f=(Px𝑥 − Px𝑥)f

ℏ s ℏ sr
= 𝑥𝑓 − H 𝑥 jk
H sk

ℏ sr sk sr
= H [𝑥 jk +𝑓 sk − 𝑥 jk]

ℏ ℏ
= H f. So, [Px, 𝑥] = H .

Quantum Mechanics/A A Mamun 8

Postulate 3-II: The set of all eigenfunctions of any operator associated with an observable
forms a "complete set”. This second part of the postulate is also called the "superposition"
principle. Thus, an arbitrary state Ψ can be expanded in a complete set of eigenvectors:
Ψ = ∑O CO ΨO
and we can also write an eigenvalue equation as
$Ψn =αn Ψn
A
We only know in this case that the measurement of physical observable 𝓪 will yield one of
the values αn, but we don't know which one is.

However, we do know the probability that eigenvalue αn will occur: it is the absolute value
squared of the coefficient, |Cn |2 . This leads to the fourth postulate.

Now, if we compare Ψ = ∑O CO ΨO with a vector 𝐂⃗ expressed in three dimensional Cartesian

co-ordinates: 𝐂⃗=v̂ 𝐂𝐱 +x̂𝑪𝒚 + 𝒌

$𝑪𝒛 , we find that the unit vectors v̂ , x̂ and 𝒌
$ along x-, y- and z-axis

act like Ψ1 , Ψ2 , Ψ3 , and Cx , Cy, Cz, act like C1 , C2 , C3 . This is why, Ψ1 , Ψ2 , Ψ3 , etc. are known
as basis vectors, and Ψ is known as state vector.

Quantum Mechanics/A A Mamun 9

§ Hilbert Space

The set of all possible state functions of a system comprise a general vector space is called
the Hilbert space. The characteristics of the Hilbert space are as follows:
1. The sum of any two members of the space is also a member of the space.
2. The product of a number (perhaps complex) is also a member of the space.
3. Any linear combination of two members of the space (i. e. 𝜆 ~ Ψ~ + 𝜆 ? Ψ?, where 𝜆 ~
and 𝜆 ? may be complex) is also a member of the space.
We can see that these properties are generalized versions of the properties of the familiar
three-dimensional vectors in real space.

One more property is required of a set of functions before they may be considered to
comprise a vector space, and that is the existence of a scalar or “inner” product of any two
members of the space. So for three dimensional vectors in real space, this is the “dot
producti” r1 .r2 . We can, therefore, define the scalar product of the state functions Ψ~ and Ψ?
as < Ψ~,Ψ? >= ∫ Ψ~∗ Ψ?d𝜏, where d𝜏 is again the volume element, and the integral is over
all the relevant volume.

Quantum Mechanics/A A Mamun 10

§ Closure Relation
To derive closure relation, we express Ψ(r,t) at t=t0 as

Ψ(r, t0) = „ CO (t …)ΨO(r)

O
Now, <Ψ(r, t0),Ψ(r, t0)>=<∑@ C@ t … Ψ@ r , ∑O CO (t … )ΨO (r) >
∗ ∗
=∑@ ∑O ∫ C@ t … Ψ@ r CO (t …)ΨO(r) dr
∗ ∗
=∑@ ∑O C@ (t …)CO(t …) ∫ Ψ@ Ψ‡ dr,
v Thomson Atom Model
∗ (t )C t 𝛿
=∑@ ∑O 𝐶ˆ … O … ˆ‡

where 𝛿ˆ‡= ∫ Ψ@ Ψ‡∗ dr is known as Kronecker’s delta having the property:

This property leads to <Ψ(r, t0),Ψ(r, t0)>=∑‡ |Cn(𝑡… )|2=1. It means that the square of the
coefficients must add up to have 1. This is known as closure relation.

Quantum Mechanics/A A Mamun 11

Postulate 4: The average value of a large (infinite) number of measurements of a physical
$) taken at random on a state Ψ(r,t) is given by
observable 𝒶 (whose corresponding operator is A

This postulate leads to the probability interpretation of quantum mechanics. We note that for
normalized Ψ(r,t), we have <Ψ(r,t),Ψ(r,t)>=1. The average value < 𝒶 > is known as the
expectation value of the physical observable 𝒶.
v Thomson Atom Model
§ What does expectation value physically mean?
§ To define physically the expectation value <𝒶> of the physical observable 𝒶:

Quantum Mechanics/A A Mamun 12

§ Orthogonality
We suppose that we have a nondegenerate set of eigenfunctions, where one only one
eigenfunction uniquely associated with each eigenvalue. We then consider two eigenvalues an
and am of the observable a which associates an Hermitian operator A. We assume that un and um
are the eigenfunctions belonging to the different eigenvalues an and am, respectively. Thus
Aun =an un , (1)
Aum=amum . (2)
Now, multiplying the left-hand-side of (1) by 𝑢 ∗ˆ, and integrating over the appropriate region,

∫ 𝑢 ∗ˆ Aun d𝜏 =< 𝑢𝑚, Aun > =<um, 𝔞nun> =𝑎‡ <𝑢ˆ , 𝑢‡ >. (3)
v Thomson Atom ModelT
The complex conjugate of (2) is given by
𝐴∗ 𝑢∗ˆ = 𝑎ˆ 𝑢∗ˆ, (4)
where 𝑎∗ˆ = 𝑎ˆ is used since this is a measurement. Similarl y, multiplying (4) by 𝑢 ‡ from
right, and integrating over the appropriate region

∫ 𝐴∗ 𝑢∗ˆun d𝜏 = < 𝐴𝑢 ˆ , 𝑢 ‡ > =< 𝑢 ˆ , 𝐴𝑢 ‡ >= 𝑎ˆ < 𝑢 ˆ, 𝑢 ‡ >. (5)

Now from 3 and 5 , we have 𝑎‡ <𝑢 ˆ , 𝑢 ‡ >=𝑎ˆ <𝑢ˆ , 𝑢‡ >, i.e.
(𝑎‡ −𝑎ˆ )<𝑢ˆ , 𝑢‡ >=0. Since 𝑎‡ ≠ 𝑎ˆ , <𝑢ˆ , 𝑢‡ >=0. Thus, the orthogonality is proved for
the nondegenerate case.

Quantum Mechanics/A A Mamun 13

Clearly, <𝒶> is a statistical average of an infinite number of measurements of the
physical observable a. The quantity in the parenthesis (or |Cn|2 in the last expression)
may be interpreted as the probability that αn will be measured.

Postulate 5: The time evolution of Ψ(r,t) for any physical system is given by

$ Ψ(r,t)=− ℏ s˜(™,š), i. e.
Schrödinger’s equation: 𝐻 — ðš

ℏ? ℏ s˜(™,š)
[?@ 𝛻2 − $
V(r)]Ψ(r,t)= — ðš
v Thomson Atom Model

It is obvious that if we know Ψ(r,t) for any physical system at an initial time and
if the system is free of external interactions, then we can find Ψ(r,t) at other
subsequent times from this Shrödinger’s equation. This equation is very
important in quantum mechanics so is Newton’s equation of motion in classical
mechanics.

Quantum Mechanics/A A Mamun 14

Quantum Mechanics/A A Mamun 15