A

A A Mamun
Department of Physics
Jahangirnagar University
 Postulates of Quantum Mechanics
 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*ψd measures the probability that the particle lies in a volume element d 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.

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 Postulate 2: To every physical observable in classical mechanics there
corresponds to an operator in quantum mechanics.

 What is a physical observable ? A

physical observable () 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 ? An
operator is defined an instruction (viz to do something on an object (operand) or a set of
objects (domain of operands) on which the operator 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:
1. Domain of action: f1(x)=f2(x)

2. Equality: = if and only if f(x) = f(x) for every f(x).

3. Additive: =+
4. Distributive: () =+
5. Associative: =()+
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6. Operators associated with physical observables:
Physical observable Symbol () Operator ()

Position r
Momentum p

Kinetic energy T=P2/2m

Potential energy V(r)

Total energy E=T+V(r) =

Total energy E

Angular momentum )

7. Commutator: The operators and do not commute in general. The commutator

of operators and is defined as []=. However, []=0 if they commute.

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Postulate 3-I: The result of the measurement of a physical observable is one of the
eigenvalues of the operator associated with that physical observable This satisfies an
eigenvalue equation: ^
A Ψ =αΨ
where α is an eigenvalue of the operator operating on the eigenfunction or eigenstate .

 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.

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 What are linear operators?
 An operator is said to be linear if and only if [(x)+(x)]=(x)+(x), where (x) and (x), are the
functions of x. All the operators in quantum mechanics are linear.

 What are Hermitian operators?

 An operator is called Hermitian if and only if <(x), (x)>= <(x), (x)>. The Hermitian
operator has real eigenvalue:
 = and = according to the eigenvalue of equation. iff
 <, >=<,>
 <, >=< , >


 This indicates that is real, i.e. the Hermitian operator has a real eigenvalue.

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 Commutator of two operators Aand 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

1. []=1
2. [Px, ]=
3. [x, F(x)]=
4. [x, PxF(x)Px]= ]

5. [x, F(x) ]=

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 Solutions:
1. To show []=1
[]f =
=x
= f. So, []=1
2. To show [Px, ]=

[Px, ]f=(Px)f
=
=+]
= f. So, [Px, ]=.

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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:

and we can also write an eigenvalue equation as

Ψn=αnΨn
We only know in this case that the measurement of physical observable 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 with a vector expressed in three dimensional Cartesian co-ordinates:
=+we find that the unit vectors and 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.

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 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. , where and may be
complex) is also a member of the space.
e 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 and as d d
is again the volume element, and the integral is over all the relevant volume.

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

Now, <Ψ(r, t0),Ψ(r, t0)>=<

=
=,
=
 Thomson Atom Model
where = is known as Kronecker’s delta having the property:

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

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

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 <> is known as the expectation
 Thomson
value Atom observable
of the physical Model .
 What does expectation value physically mean?
 To define physically the expectation value <> of the physical observable :

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 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 u n and um
are the eigenfunctions belonging to the different eigenvalues an and am, respectively. Thus

Aun=anun , (1)

Aum=amum . (2)
Now, multiplying the left-hand-side of (1) by , and integrating over the appropriate region,
und> . (3)
 Thomson Atom ModelT
The complex conjugate of (2) is given by
, (4)
where y, multiplying (4) by from right, and integrating over the appropriate region
u nd
Now =, i.e.
=0. Since =0. Thus, the orthogonality is proved for the nondegenerate case.

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Clearly, <> is a statistical average of an infinite number of measurements of the
physical observable a. The quantity in the parenthesis (or |C n|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
Schrödinger’s equation:(r,t)=, i. e.
[]r,t)=
 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.

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