Operators, Eigenfunctions and

Eigenvalues

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 Observables and operators

Consider four basic postulates of quantum mechanics that

serve to formalize the rules of quantum mechanics

1 Postulate I

To any self-consistently and well defined observable in physics

(call it A), such as linear momentum, energy, mass angular
momentum, or number of particles, there corresponds an
operator (call it 𝐴) such that measurement of A yields values
(call these measured values a) which are eigenvalues of 𝐴

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 The values, a, are those values for which the equation has a
solution

(a) 𝑨𝝋 = 𝒂𝝋 Eigenvalue equation

The function 𝝋 is called the eigenfunction of 𝐴 corresponding

to the eigenvalue a

Consider the momentum operator 𝑝 that corresponds to

observable linear momentum as follows: 𝑝 = −𝑖ℏ𝛻

If the particle is constrained to move in x-direction 𝑝𝑥 =

𝜕
− 𝑖ℏ
𝜕𝑥

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(b) 𝜕
The eigenvalue equation for this operator is −𝑖ℏ 𝜑 = 𝑝𝑥 𝜑
𝜕𝑥

The values 𝑝𝑥 represent the only possible values that

measurement of the x component of momentum will yield. The
𝜕
eigenfunction is 𝜑 and the operator is 𝑝𝑥 = −𝑖ℏ
𝜕𝑥

Suppose the particle was free along the x-axis, with no

boundary conditions on 𝝋

(c) 𝒊𝒑𝒙 𝒙
The solution to (b) would be 𝝋 = 𝑨 𝒆𝒙𝒑 = 𝑨𝒆𝒊𝒌𝒙
ℏ

(d) Substituted the wave number k = 𝑝 and deleted subscript x

ℏ

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(e) The eigenfunction (c) is periodic function in x. to find its
wavelength 𝜆, set 𝑒 𝑖𝑘𝑥 = 𝑒 𝑖𝑘(𝑥+𝜆)

1 = 𝑒 𝑖𝑘𝜆 = 𝑐𝑜𝑠𝑘𝜆 + 𝑖𝑠𝑖𝑛𝑘𝜆 which is satisfied if

cos 𝑘𝜆 = 1 𝑎𝑛𝑑 sin 𝑘𝜆 = 0

The 1st non vanishing solution is 𝑘𝜆 = 2𝜋 which in combination

ℎ
with equation (d) we get 𝑝 = which is the de Broglie relation
𝜆

The eigenfunction of the momentum operator corresponding

to the eigenvalue p has wavelength that is deBroglie
𝒉
wavelength
𝒑

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(f) The operator corresponding to the energy is the Hamiltonian 𝐻

For a single particle of mass m, potential field V(r), the

𝑝2 ℏ2 2
eigenvalue equation is 𝐻 = +𝑉 𝑟 = − 𝛻 + 𝑉 𝑟 or
2𝑚 2𝑚

𝐻 𝜑 𝑟 = 𝐸𝜑(𝑟)

The equation is called the time-independent Schroedinger

equation

Consider s free particle with motion in one dimension

ℏ2 𝜕 2 2𝑚𝐸
− 𝜑 = 𝐸𝜑, using the wave vector, 𝑘 2 = the eqn
2𝑚 𝜕𝑥 2 ℏ2

becomes
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 𝑑2 𝜑
+ 𝑘2𝜑 = 0
𝑑𝑥 2

(g) For free particle, there are no boundary conditions, soln is

𝛗 = 𝑨𝒆𝒊𝒌𝒙 + 𝑩𝒆−𝒊𝒌𝒙 which is an eigenfunction of 𝑯
ℏ2 𝑘 2
corresponds to the energy eigenvalue 𝐸 =
2𝑚

The eigenfunction of 𝑯 and with B=0, is also an eigenfunction of

𝒑

Let 𝑝𝝋 = ℏ𝒌𝝋 and if 𝝋 is also an eigenfunction of 𝑯 (for free

𝑝𝟐 𝑝 𝑝 ℏ𝑘𝜑 ℏ𝒌 ℏ𝒌 𝟐
particle), 𝑯𝝋 = 𝝋 = 𝑝𝜑 = = 𝑝𝜑 = 𝝋
𝟐𝒎 𝟐𝒎 𝟐𝒎 𝟐𝒎 𝟐𝒎

It shows that 𝝋 is also an eigenfunction

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of 𝑯 7
 Both the energy and momentum eigenvalues for free particle
ℏ2 𝑘 2
comprise a continuum of values 𝐸 = ; 𝑝 = ℏ𝑘
2𝑚

(h) The eigenfunction of both 𝑯 and 𝒑 corresponding to these

eigenvalues is 𝝋𝒌 = 𝑨𝒆𝒊𝒌𝒙

If the free particle is in this state, measurement of its momentum

ℏ𝟐 𝒌𝟐
will yield ℏ𝒌 and measurement of its energy will yield
𝟐𝒎

If the particle is in the state, the probability density relating to the

probability of finding the particle in the interval x, x+dx is
𝝋𝒌 𝟐 = 𝑨 𝟐 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕. The probability density is the same for
all x.
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 We would be equally likely to find a particle at any point within
− ∞ ≤ 𝑥 ≤ ∞.

(i) In the state 𝝋𝒌 , it is known with absolute certainty that

measurement of momentum yields ℏ𝒌

Therefore, for the state 𝝋𝒌 , ∆𝒑 = 𝟎, 𝒘𝒉𝒆𝒏𝒄𝒆 ∆𝒙 = ∞

This is a statement of maximum uncertainty in agreement with

the Heisenberg uncertainty principle: ∆x∆𝑝𝑥 ≥ ℏ

(j) POSTULATE II

Measurement of the observable A that yields the value a leaves

the system in the state 𝝋𝒂 , where 𝝋𝒂 is the eigen function of
that corresponds to the eigenvalue
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In the
The first
eigenfunction
two postulates
of the
state that 𝑥 corresponding to
operator
eigenvalue 𝑥
There is an operator corresponding to the measurement of
The operator
position, 𝑥.
call itequation appears as follows:
𝑥 𝛿 𝑥 − 𝑥 ′ = 𝑥,𝛿 𝑥 − 𝑥′
Measurement of x that yields the value
𝑥 , , leaves the particle

In the eigenfunction of the operator 𝑥 corresponding to

eigenvalue 𝑥

The operator equation appears as follows:

𝑥𝛿 𝑥 − 𝑥 ′ = 𝑥 , 𝛿 𝑥 − 𝑥 ′

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(k) The eigenfunction of 𝑥 has been written 𝛿 𝑥 − 𝑥 ′ , it is the
Dirac delta function. It is defined as follows:
∞
−∞
𝑓 𝑥 ′ 𝛿 𝑥 − 𝑥 ′ 𝑑𝑥 ′ = 𝑓(𝑥) or
∞
−∞
𝑓 𝑦 𝛿 𝑦 𝑑𝑦 = 𝑓(0)
∞ ∞
−∞
𝛿 𝑥 − 𝑥′ 𝑑𝑥 ′ =1 or −∞
𝛿 𝑦 𝑑𝑦 = 1

𝛿 𝑦 = 0 (𝑓𝑜𝑟 𝑦 ≠ 0)

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(l) POSTULATE III:

The state of a system at any instant of time may be represented

by a state or wave function which is continuous and
differentiable. All information regarding the state of a system is
contained in the wave function.

If a system is in state 𝜓(r,t) , the average of any physical

observable C relevant to that system at time t is 𝐶 =

𝜓 ∗ 𝐶 𝜓𝑑𝑟

The average 𝐶 is called the expectation value of C

1 𝑁
The average of C is given by 𝐶 = 𝑖=1 𝐶𝑖 for N≫ 1
𝑁
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Another way of defining 𝐶 is in terms of the probability
𝑃 𝐶𝑖 , the probability that measurement of C finds value 𝐶𝑖

𝐶 = 𝑎𝑙𝑙 𝐶 𝐶𝑖 𝑃 𝐶𝑖 . If the values of C comprise a continuous

set, the value of 𝐶 becomes as follows 𝐶 = 𝐶 𝑃 𝐶 𝑑𝐶

𝜓 2 𝑑𝐶 = 𝑃 𝐶 𝑑𝐶

The probability of finding the particle in the interval x, x+dx is

∞ ∞ ∗ 𝐶 𝜓 𝑑𝐶
𝐶 = −∞
𝐶𝑃(𝐶) 𝑑𝐶 = −∞
𝜓

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(m) Postulate IV: the state function for a system (e.g, a single
particle) develops in time according to the equation

𝜕
𝑖ℏ 𝜓 𝑟, 𝑡 = 𝐻 𝜓 𝑟, 𝑡 : The time-dep. Schroedinger eqn
𝜕𝑡

Using separation of variables 𝜓 𝑟, 𝑡 = 𝜑 𝑟 𝑇(𝑡). Substituting

in the time-dependent Schroedinger eqn to get

𝑇𝑡 𝐻𝜑 𝜕𝑇
𝑖ℏ = and 𝑇𝑡 =
𝑇 𝜑 𝜕𝑡

The equation can be satisfied only if both sides are equal to the
same constant, call it E. Therefore, we get

𝐻 𝜑(𝑟) = 𝐸𝜑(𝑟): Time-independent Schroedinger eqn

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𝜕 𝑖𝐸 𝑖𝐸𝑡
+ 𝑇 𝑡 =0 ⟹ 𝑇 𝑡 = 𝐴𝑒𝑥𝑝 −
𝜕𝑡 ℏ ℏ

𝑖𝐸𝑛 𝑡
𝜓𝑛 𝑟, 𝑡 = 𝐴𝜑𝑛 𝑒𝑥𝑝 −
ℏ

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 Particle in a box

Consider a particle in a box given below

The corresponding potential values are

V(x) = ∞ (x≤0, x≥L Domain 1

V(x)=0 (0<x<L) Domain 2

Hamiltonian for this problem is

𝑝2 (x≤0, x≥L Domain 1

𝐻1 = +∞=∞
2𝑚

𝑝2 (0<x<L) Domain 2
𝐻2 =
2𝑚

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In domain 1, the time-independent Schroedinger equation gives
ϕ = 0. for any finite eigen energy E, in this domain the equation
gives

𝐻1 𝜑 = 𝐸𝜑.

The fact that 𝜑 = 0 in domain 1 implies that there is a zero

2
probability that the particle is found there ( 𝜑 = 0)

ℏ2 𝜕 2
In domain 2, the Schroedinger eqn is − 𝜑 = 𝐸𝑛 𝜑𝑛
2𝑚 𝜕𝑥 2 𝑛

Since is a continuous function, it must have 𝜑𝑛 (0) = 𝜑𝑛 (𝐿) = 0

2𝑚𝐸𝑛 𝜕2 𝜑𝑛
Let 𝑘2 𝑛 = 𝑎𝑛𝑑 𝑠𝑜 + 𝑘𝑛 2 𝜑𝑛 = 0
ℏ2 𝜕𝑥 2
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Therefore the solution would be 𝜑𝑛 = 𝐴 𝑠𝑖𝑛𝑘𝑛 𝑥 + 𝐵 cos 𝑘𝑛 𝑥

The boundary conditions give the following B = 0 and

A sink n L = 0

𝐴 𝑠𝑖𝑛𝑘𝑛 𝐿 = 0 ⟹ 𝑘𝑛 𝐿 = 𝑛𝜋 where n=0,1,2,

Normalization conditions
𝐿 2 𝐿 2 𝑛𝜋𝑥
⟹ 0
𝜑 𝑛 𝑑𝑥 = 1 = 𝐴2 0
𝑠𝑖𝑛 𝑑𝑥
𝐿

𝐴2 𝐿 𝐿 2 𝐴2 𝐿 𝑛𝜋𝑥
1= 𝑠𝑖𝑛 𝜃 𝑑𝜃 = ⟹𝜃=
𝑛𝜋 0 2 𝐿

ℏ2 𝑘1 2 ℏ2 𝜋 2 2 𝑛𝜋𝑥
𝐸𝑛 = 𝑛2 𝐸1 𝑎𝑛𝑑 𝐸1 = = and 𝜑𝑛 = 𝑠𝑖𝑛
2𝑚 2𝑚𝐿2 𝐿 𝐿
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The Bohr correspondence Principle: A quantum mechanical
result must reduce to its classical counterpart in the classical
domain.

Since classical formulas do not contain ℏ, such transition

should be realized in the limit that ℏ becomes small.

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 DIRAC NOTATION

(a) A product of two state functions, 𝜓 𝑥 𝑎𝑛𝑑 𝜑 𝑥 𝑖𝑠 𝑔𝑖𝑣𝑒𝑛 𝑎𝑠

∞ ∗ (𝑥)𝜑(𝑥) 𝑑𝑥
𝜓𝜑 = −∞
𝜓

(b) The integral operation 𝜓 𝜑 denotes:

Take the complex conjugate of the object in the 1st slot

(𝜓 ⟶ 𝜓 ∗ )

(c) Integrate the product 𝜓 ∗ 𝜑

If a is any complex number and the functions 𝜓 𝑎𝑛𝑑 𝜑 are such

∞ ∗ 𝜑𝑑𝑥
that −∞
𝜓 < ∞ the following rules hold:
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 The rules in the Dirac notation

(a) 𝜓 ≡ 𝑏𝑟𝑎 𝑣𝑒𝑐𝑡𝑜𝑟, 𝜑 ≡ 𝑘𝑒𝑡 𝑣𝑒𝑐𝑡𝑜𝑟 𝑎𝑛𝑑 𝜓 𝜑 ≡ 𝑏𝑟𝑎𝑘𝑒𝑡

(b) 𝜓 𝒂𝜑 = 𝑎 𝜓 𝜑

(c) 𝑎𝜓 𝜑 = 𝑎∗ 𝜓 𝜑

(d) 𝜓𝜑 ∗ = 𝜑𝜓

(e) 𝜑+𝜓 = 𝜓 + 𝜑

(f) 𝜓1 + 𝜓2 ∗ 𝜑1 + 𝜑2 𝑑𝑥 = 𝜓1 + 𝜓2 𝜑1 + 𝜑2

= 𝜓1 + 𝜓2 𝜑1 + 𝜑2
= 𝜓1 𝜑1 + 𝜓1 𝜑2 + 𝜓2 𝜑1 + 𝜓2 𝜑2

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