Module 3 : Postulates of Quantum

Mechanics
(Lecture Notes for Engineering Physics : BAPHY105)

Vishnudath K N
Assistant Professor
Department of Physics, School of Advanced Sciences
VIT Vellore
2

Disclaimer
These lecture notes do not claim originality. They are an assimilation of existing materials
from various standard textbooks and lecture notes, compiled and reorganized to suit the
structure and requirements of the course syllabus.

Note
These lecture notes are continuously updated based on classroom discussions and ques-
tions asked by students. There may still be mistakes, and if you find any, please feel free
to write to me at [Link]@[Link].
Contents

3 Postulates of Quantum Mechanics 4

3.1 States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2 Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.1 Spin Operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.2 Position, Momentum, and Energy Operators . . . . . . . . . . . . 6
3.3 Interlude : Classical Probability . . . . . . . . . . . . . . . . . . . . . . . 7
3.4 Quantum Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.4.1 Observables and Expectation Values . . . . . . . . . . . . . . . . 10
3.5 Foundational Consequences of the Measurement Postulate . . . . . . . . 14
3.5.1 Sequential Stern–Gerlach Experiment . . . . . . . . . . . . . . . . 14
3.5.2 Non-Commuting Operators and Their Implications . . . . . . . . 16
3.6 Time Evolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.6.1 Time-Dependent Schrödinger Equation . . . . . . . . . . . . . . . 19
3.6.2 Time-Independent Schrödinger Equation . . . . . . . . . . . . . . 19

3
Module 3

Postulates of Quantum Mechanics

In this module, we will study the postulates of quantum mechanics, which are the foun-
dational principles that describe how microscopic systems behave. Remember that these
postulates are not derived from any fundamental principle; rather, they are accepted
because they successfully explain experimental observations.
After discussing the postulates of quantum mechanics, we will see them in action both
in this module and in the next. So let us get into business without further fuss.

3.1 States

Postulate 1: The state of a physical system is completely described by a normal-

ized state vector in a complex Hilbert space. The mathematical form of this vector
depends on the physical system under consideration. Different physical systems
therefore correspond to different Hilbert spaces.

Example 1: Spin state of an electron Consider an electron whose spin is measured

along the z-axis. The spin state is described by a vector in a two-dimensional complex
Hilbert space.
We choose the orthonormal basis
   
1 0
|0⟩ = , |1⟩ = .
0 1
An arbitrary spin state can then be written as
|χ⟩ = α|0⟩ + β|1⟩, α, β ∈ C, (3.1)
or equivalently as the column vector
 
α
|χ⟩ = .
β
The normalization condition requires
|α|2 + |β|2 = 1.
Thus, the spin state belongs to the finite-dimensional Hilbert space C2 .

4
3.2. OPERATORS 5

Example 2: Particle in one dimension Unlike the spin system, which is described
by a finite-dimensional Hilbert space, the state of a particle moving in one dimension is
represented by a wave function Ψ(x, t).
As we have seen in Module 1, the wave function is a complex-valued function that
satisfies the time-dependent Schrödinger equation:
∂Ψ(x, t) ℏ2 ∂ 2 Ψ(x, t)
iℏ =− + V (x)Ψ(x, t), (3.2)
∂t 2m ∂x2
where m is the particle mass and V (x) is the potential energy.

Born Rule and Normalization

The probability density for finding the particle at position x and time t is
ρ(x, t) = |Ψ(x, t)|2 . (3.3)
Therefore, the probability of finding the particle between a and b is
Z b
P (a ≤ x ≤ b) = |Ψ(x, t)|2 dx, (3.4)
a

with the normalization condition

Z ∞
|Ψ(x, t)|2 dx = 1. (3.5)
−∞

The wave function thus belongs to the Hilbert space L2 (R), the space of square-
integrable complex functions.

3.2 Operators

Postulate 2: Every measurable physical quantity (observable) is represented by

a Hermitian operator acting on the Hilbert space of the system. The possible
outcomes of a measurement are the eigenvalues of the corresponding operator.

The explicit mathematical form of an operator depends on the representation chosen

for the state vector.

3.2.1 Spin Operators

For a spin- 12 system, the components of the spin angular momentum are represented by
the operators
ℏ
Ŝi = σi , i = x, y, z, (3.6)
2
where σi are the Pauli matrices:
     
0 1 0 −i 1 0
σx = , σy = , σz = . (3.7)
1 0 i 0 0 −1
These operators act on vectors in the Hilbert space C2 .
While spin operators act on a finite-dimensional Hilbert space, operators for a particle
moving in space act on wave functions and are therefore differential operators.
6 MODULE 3. POSTULATES OF QUANTUM MECHANICS

3.2.2 Position, Momentum, and Energy Operators

In the position representation, the operators take the form

Position operator: x̂ = x,
∂
Momentum operator: p̂x = −iℏ
, (3.8)
∂x
2 2
ℏ ∂
Hamiltonian operator: Ĥ = − + V (x).
2m ∂x2
The Hamiltonian operator corresponds to the total energy of the system, and its
explicit form depends on the physical system under consideration.
For a particle moving in one dimension under the influence of a potential V (x), the
classical expression for the total energy is

p2
E= + V (x). (3.9)
2m
Motivated by the classical expression, we can construct the quantum Hamiltonian by
promoting x and p to operators.
Here we assume that the particle moves only along the x-direction. The extension to
three dimensions is straightforward.

Exercise
Show that the momentum operator is Hermitian.

Solution
We check whether the momentum operator
d
p̂ = − iℏ (3.10)
dx
is Hermitian. By definition, p̂ is Hermitian if

⟨f |p̂|g⟩ = ⟨g|p̂|f ⟩∗ (3.11)

for all suitable wave functions f, g (Remember the definition of Hermitian operator from
Module 2.).
Compute1 : Z ∞  dg 
⟨f |p̂|g⟩ = f ∗ (x) − iℏ dx. (3.12)
−∞ dx
Integrating by parts,
df ∗
Z i∞ Z
∗ dg h
∗
f (x) dx = f (x)g(x) − g(x) dx. (3.13)
dx −∞ dx
1
Note that for wave functions in L2 , the inner product is
Z
⟨f |g⟩ = f ∗ (x)g(x) dx.

Thus ⟨f |p̂|g⟩ means that we insert p̂ between the bra and ket before computing the integral.
3.3. INTERLUDE : CLASSICAL PROBABILITY 7

Therefore,
∞
df ∗ 
h i∞ Z 
∗
⟨f |p̂|g⟩ = − iℏf (x)g(x) + iℏ g(x) dx. (3.14)
−∞ −∞ dx
For physical (square-integrable) wave functions that vanish sufficiently fast at infinity,
the first term is zero. Hence
Z ∞
df ∗
⟨f |p̂|g⟩ = − iℏ g(x) dx = ⟨g|p̂|f ⟩∗ . (3.15)
−∞ dx
Thus
p̂† = p̂, (3.16)
and the momentum operator is Hermitian.

3.3 Interlude : Classical Probability

Quantum mechanics is intrinsically probabilistic. To understand the measurement pos-
tulates, we briefly review the basic ideas of classical probability.

Discrete Random Variables

Suppose we have a collection of possible outcomes, such as the ages of students in a class,
or the outcome of rolling a die. A variable j that can take only certain isolated values
(for example j = 14, 15, 16, . . . for ages, or j = 1, 2, 3, 4, 5, 6 for a die) is called a discrete
random variable.

• N (j): the number of individuals or outcomes with value j (a count taken from the
sample).

• N : the total number of individuals in the sample,

X
N= N (j). (3.17)
j

• P (j): the probability that a randomly chosen outcome has value j. It is defined by
N (j)
P (j) = . (3.18)
N
Because some outcome must occur, the probabilities satisfy
X
P (j) = 1. (3.19)
j

Mean (Expectation Value) : The mean or expectation value of j is

X
⟨j⟩ = j P (j). (3.20)
j

This is the average value one would obtain by repeating the experiment many times and
averaging the results.
8 MODULE 3. POSTULATES OF QUANTUM MECHANICS

Median : The median is the value of j such that half the outcomes are smaller and
half are larger. It measures the middle of the distribution and is insensitive to extreme
outliers.

Most Probable Value : The value of j for which P (j) is maximum. It is the single
value most likely to be observed in one trial.

Variance and Standard Deviation : The variance measures the spread or ”width”
of the distribution about the mean. It is defined as the mean of the squared deviations
from the mean: X
σ 2 = (j − ⟨j⟩)2 = (j − ⟨j⟩)2 P (j). (3.21)
j

Because the deviations are squared, the variance is always positive. The standard devia-
tion, √
σ = σ2, (3.22)
is the square root of the variance and has the same units as j; it is the customary measure
of typical deviation from the mean.

Useful identity : It is often convenient to compute the variance using

X
σ 2 = ⟨j 2 ⟩ − ⟨j⟩2 , where ⟨j 2 ⟩ = j 2 P (j). (3.23)
j

Worked example (discrete) : A class contains N = 14 students with ages distributed

as follows:
age j 14 15 16 22 24 25
(3.24)
N (j) 1 1 3 2 2 5
Thus the probabilities are
P (j) = N (j)/14.
Compute the mean:
X 1 · 14 + 1 · 15 + 3 · 16 + 2 · 22 + 2 · 24 + 5 · 25 294
⟨j⟩ = jP (j) = = = 21. (3.25)
j
14 14

Compute ⟨j 2 ⟩:
X 1 · 142 + 1 · 152 + 3 · 162 + 2 · 222 + 2 · 242 + 5 · 252
⟨j 2 ⟩ = j 2 P (j) = . (3.26)
j
14

Evaluating each term:

142 · 1 = 196, 152 · 1 = 225, 162 · 3 = 3 × 256 = 768,

(3.27)
222 · 2 = 2 × 484 = 968, 242 · 2 = 2 × 576 = 1152, 252 · 5 = 5 × 625 = 3125.

Sum of numerators = 196 + 225 + 768 + 968 + 1152 + 3125 = 6434. Therefore
6434 3217
⟨j 2 ⟩ = = ≈ 459.5714286. (3.28)
14 7
3.4. QUANTUM MEASUREMENT 9

Now the variance:

3217 3217 3087 130
σ 2 = ⟨j 2 ⟩ − ⟨j⟩2 = − 212 = − = ≈ 18.57142857. (3.29)
7 7 7 7
The standard deviation is
√
r
130
σ= σ2 = ≈ 4.3095. (3.30)
7
So, for this class distribution:
130
⟨j⟩ = 21, σ2 = ≈ 18.57, σ ≈ 4.31. (3.31)
7

Continuous Random Variables

If the variable x can take any real value, we describe it by a probability density function
ρ(x) such that the probability for x to take any value between a and b is
Z b
P (a ≤ x ≤ b) = ρ(x) dx (3.32)
a

Further, the sum of probabilities equaling to 1 implies

Z ∞
ρ(x) dx = 1. (3.33)
−∞

Expectation values are

Z ∞ Z ∞
⟨x⟩ = x ρ(x) dx, ⟨f (x)⟩ = f (x) ρ(x) dx, (3.34)
−∞ −∞

and the variance is

σ 2 = ⟨(x − ⟨x⟩)2 ⟩ = ⟨x2 ⟩ − ⟨x⟩2 . (3.35)

3.4 Quantum Measurement

Postulate 3: When a physical observable corresponding to a Hermitian operator

 is measured, the only possible outcomes are the eigenvalues of Â.
If the system is in a normalized state |ψ⟩, the probability of obtaining the eigenvalue
an is

P (an ) = |⟨an |ψ⟩|2 ,

where |an ⟩ is the eigenvector associated with an .

Postulate 4 (State Collapse): Immediately after a measurement yielding the

eigenvalue an , the system collapses to the corresponding eigenstate |an ⟩.

Thus, quantum measurement is inherently probabilistic: even with complete knowl-

edge of the quantum state, only the probabilities of different outcomes can be predicted,
never the exact result of a single measurement.
10 MODULE 3. POSTULATES OF QUANTUM MECHANICS

Example
As an example, let us consider the spin operator along the z-axis:
 
ℏ 1 0
Ŝz = . (3.36)
2 0 −1

The eigenvalues and eigenvectors are

Ŝz |0⟩ = + ℏ2 |0⟩, Ŝz |1⟩ = − ℏ2 |1⟩. (3.37)

Thus, |0⟩ and |1⟩ represent spin up and spin down along the z axis, with outcomes
+ℏ/2 and −ℏ/2 respectively.
Physically, this means if we send an electron through a Stern-Gerlach apparatus
aligned along z, it will always deflect either up or down, not somewhere in between.
Thus, a general spin state is a linear combination:

|ψ⟩ = α|0⟩ + β|1⟩, |α|2 + |β|2 = 1. (3.38)

When we measure Ŝz , the possible outcomes are +ℏ/2 and −ℏ/2. The probabilities are

P + ℏ2 = |⟨0|ψ⟩|2 = |α|2 , P − ℏ2 = |⟨1|ψ⟩|2 = |β|2 .

(3.39)

In other words, |α|2 tells us the chance that the spin is measured up, and |β|2 the
chance it is measured down.

Repeated measurements on identically prepared systems reveal the probability distribution

predicted by quantum mechanics.

Collapse of the Wave Function

Immediately after measurement, the state collapses to the corresponding eigenstate:
(
|0⟩ with probability |α|2 ,
|ψ⟩ −→ (3.40)
|1⟩ with probability |β|2 .

This means that once we actually observe the spin, the superposition disappears and
the particle is definitely in either the up or the down state.

3.4.1 Observables and Expectation Values

While a single measurement yields one of the eigenvalues, the expectation value represents
the average result obtained from many measurements performed on identically prepared
systems.

Expectation value of position

By analogy with classical probability the mean position of a particle with wave function
ψ(x, t) is given as, Z ∞
⟨x⟩ = x |ψ(x, t)|2 dx. (3.41)
−∞
3.4. QUANTUM MEASUREMENT 11

where |ψ(x, t)|2 is the probability density ρ(x, t).

In general, the expectation value of an operator Q̂ in the state |ψ⟩ is defined as

⟨ψ|Q̂|ψ⟩
⟨Q̂⟩ψ = . (3.42)
⟨ψ|ψ⟩
In what follows, we will assume that all states are properly normalized, so that

⟨ψ|ψ⟩ = 1.

Under this assumption, the expectation value simplifies to

⟨Q̂⟩ = ⟨ψ|Q̂|ψ⟩. (3.43)

As we have seen before, the bra-ket notation translates into integrals when the Hilbert
space is spanned by continuous wavefunctions ψ(x):
Z ∞
⟨ψ|Q̂|ψ⟩ = ψ ∗ (x) Q̂ ψ(x) dx. (3.44)
−∞

For example:
• If Q̂ = x̂, then Z ∞
⟨x⟩ = ψ ∗ (x) x ψ(x) dx. (3.45)
−∞

• If Q̂ = p̂ = −iℏ dx
d
, then
Z ∞
∗ d
⟨p⟩ = ψ (x) − iℏ ψ(x) dx. (3.46)
−∞ dx

Thus, in discrete Hilbert spaces, we use sums, while in continuous spaces, we use
integrals.

Example : Expectation Value in a Two-State System

Consider a two-dimensional Hilbert space with orthonormal basis vectors
   
1 0
|0⟩ = , |1⟩ = . (3.47)
0 1

A general state vector in this space can be written as

|ψ⟩ = α|0⟩ + β|1⟩, with |α|2 + |β|2 = 1. (3.48)

Let us consider a general Hermitian operator

 
a b
 = ∗ , a, d ∈ R, b ∈ C. (3.49)
b d

The expectation value of  in the state |ψ⟩ is

⟨Â⟩ψ = ⟨ψ|Â|ψ⟩. (3.50)

12 MODULE 3. POSTULATES OF QUANTUM MECHANICS

Explicitly,
 
∗ ∗ aα + bβ
⟨ψ| = (α , β ), Â|ψ⟩ = ∗ . (3.51)
b α + dβ

Thus,
⟨ψ|Â|ψ⟩ = α∗ (aα + bβ) + β ∗ (b∗ α + dβ). (3.52)

Simplifying,
⟨Â⟩ψ = a|α|2 + d|β|2 + α∗ bβ + β ∗ b∗ α (3.53)

which is always real, as expected for a Hermitian operator.

Physical Intuition

The difference between a single measurement and an expectation value is crucial. A single
measurement of Ŝz will always give either +ℏ/2 or −ℏ/2. However, if we prepare many
identical systems in the same state |ψ⟩ and measure Ŝz on each of them, then the average
of all the outcomes will approach the expectation value

ℏ
|α|2 − |β|2 .


2

Verify that this is indeed the expectation value of Ŝz = ℏ2 σz in a general state
|ψ⟩ = α|0⟩ + β|1⟩.

Exercises
The following exercises are designed to strengthen your understanding of probability,
expectation values, and measurements before we proceed to the dynamics of quantum
systems.

Exercise 1
A fair six sided die is rolled once.

1. Write down the probability distribution P (j) for j = 1, 2, 3, 4, 5, 6.

2. Compute the expectation value ⟨j⟩.

3. Compute the variance σ 2 .

Hint: Each outcome has probability 1/6. Use the formulas

X
⟨j⟩ = jP (j), σ 2 = ⟨j 2 ⟩ − ⟨j⟩2 .
j
3.4. QUANTUM MEASUREMENT 13

Exercise 2
Consider the normalized probability density

1 2
ρ(x) = √ e−x , −∞ < x < ∞.
π
R∞
1. Verify that −∞
ρ(x) dx = 1.

2. Compute the expectation value ⟨x⟩.

3. Compute ⟨x2 ⟩ and hence the variance σ 2 .

Hint: Use the Gaussian integrals

∞ ∞ √
√
Z Z
−x2 2 −x2 π
e dx = π, xe dx = .
−∞ −∞ 2

Exercise 3
Let the wave function of a particle be
(q
3
2a3
(a − |x|), |x| ≤ a,
ψ(x) =
0, |x| > a,

where a > 0 is a constant.

1. Verify that ψ(x) is normalized.

2. Compute the expectation value ⟨x⟩.

3. Compute the expectation value ⟨x2 ⟩.

Hint: The wave function is an even function of x. Think about what this means for
⟨x⟩.

Exercise 4
A spin- 21 particle is in the state

1
q
2
|ψ⟩ = √ |0⟩ + 3
|1⟩.
3

1. What are the probabilities of measuring +ℏ/2 and −ℏ/2 for Ŝz ?

2. Compute the expectation value ⟨Ŝz ⟩.

Hint: Recall that P (+ℏ/2) = |α|2 and P (−ℏ/2) = |β|2 when |ψ⟩ = α|0⟩ + β|1⟩.
14 MODULE 3. POSTULATES OF QUANTUM MECHANICS

Exercise 5
Let  
2 1 1

 = , |ψ⟩ = √ |0⟩ + |1⟩ .
1 3 2

1. Compute ⟨Â⟩ψ .

2. Verify explicitly that the result is real.

Hint: Write |ψ⟩ in column vector form and perform the matrix multiplication step
by step.

3.5 Foundational Consequences of the Measurement

Postulate
3.5.1 Sequential Stern–Gerlach Experiment
The Stern–Gerlach experiment demonstrates the quantization of spin angular momentum.
The sequential Stern-Gerlach experiment provides a direct physical illustration of the
measurement postulate and the superposition principle.
For a spin- 21 particle, the spin operators are related to the Pauli matrices:

ℏ
Ŝi = σi , i = x, y, z,
2

with eigenvalues ± ℏ2 . The Pauli matrices are

     
0 1 0 −i 1 0
σx = , σy = , σz = .
1 0 i 0 0 −1

Eigenstates along z
The eigenvectors of σz are
   
1 0
|+z⟩ = , |−z⟩ = .
0 1

These correspond to “spin up” and “spin down” along the z-axis.

Eigenstates along x
The eigenvectors of σx can be written in terms of the z-basis:
 
1 1 1

|+x⟩ = √ = √ |+z⟩ + |−z⟩ ,
2 1 2
 
1 1 1

|−x⟩ = √ = √ |+z⟩ − |−z⟩ .
2 −1 2
3.5. FOUNDATIONAL CONSEQUENCES OF THE MEASUREMENT POSTULATE15

Eigenstates along y
The eigenvectors of σy are
 
1 1 1

|+y⟩ = √ = √ |+z⟩ + i |−z⟩ ,
2 i 2
 
1 1 1

|−y⟩ = √ = √ |+z⟩ − i |−z⟩ .
2 −i 2

Superposition Example
Consider the state |+z⟩. In the y-basis, it can be expanded as
1

|+z⟩ = √ |+y⟩ + |−y⟩ .
2
This means that a particle prepared in the | + z⟩ spin state has equal probability of being
found in |+y⟩ or |−y⟩ when measured along the y-axis. Explicitly,
1 1
P (+y) = |⟨+y| + z⟩|2 = , P (−y) = |⟨−y| + z⟩|2 = .
2 2

Sequential Stern–Gerlach Setup

As in the Stern–Gerlach (SG) experiment, we produce a beam of silver atoms by heating
them to a very high temperature in an oven. This beam is initially unpolarized (its spin
state is undetermined). It is then passed through a series of SG apparatuses in which
the external non-uniform magnetic field is aligned along different directions, as described
below:

1. First SG apparatus (along z): The unpolarized beam splits into |+z⟩ and |−z⟩
components.

2. Second SG apparatus (along x): Select the |+z⟩ beam and pass it through an
SG apparatus aligned along x. It splits into |+x⟩ and |−x⟩, each with probability
1
2
.

3. Third SG apparatus (again along z): Select the |+x⟩ beam and pass it through
an SG apparatus aligned along z. It splits again into |+z⟩ and |−z⟩, each with
probability 21 .

Key points:
• Measurement collapses the state into an eigenstate of the chosen observable.

• A definite state along one axis is a superposition of states along another.

• The spin operators along different axes do not commute: [Ŝz , Ŝx ] = iℏŜy . One can
not define common eigenvectors for non-commuting operators.

• Sequential measurements reveal the probabilistic and non-commuting nature of

quantum observables.
16 MODULE 3. POSTULATES OF QUANTUM MECHANICS

Figure 3.1: Schematic of the sequential Stern–Gerlach experiment: (a) a first SG appara-
tus splits the beam along z, (b) the selected |+z⟩ beam is sent through a second SG along
x, and (c) finally one of the outputs is measured again along z. (Adapted from Modern
Quantum Mechanics by J. J. Sakurai and Jim Napolitano, 2nd edition, for instructional
use only.)

3.5.2 Non-Commuting Operators and Their Implications

In quantum mechanics, physical observables are represented by operators. Two operators
 and B̂ are said to commute if

[Â, B̂] = ÂB̂ − B̂ Â = 0.

If the commutator vanishes, the operators share a common set of eigenstates and the
corresponding observables can be measured simultaneously with certainty. If the com-
mutator is non-zero, the observables are incompatible: measuring one disturbs the
outcome of the other.

Sequential Measurements and Non-Commutativity

The sequential Stern–Gerlach experiment provides a physical example. If we measure

spin along the z axis and immediately measure again along z, the outcome is definite
and reproducible. But if we measure first along z and then along x, the second measure-
ment randomizes the result. Mathematically, this corresponds to the fact that the spin
operators do not commute:
[Sz , Sx ] = iℏSy ̸= 0.

Thus, the order of measurements matters whenever operators do not commute.

3.5. FOUNDATIONAL CONSEQUENCES OF THE MEASUREMENT POSTULATE17

Uncertainty Relations
Non-commuting operators lead directly to the uncertainty principle. Consider two Her-
mitian operators  and B̂. Define the variances (uncertainties)

(∆A)2 = ⟨(Â − ⟨Â⟩)2 ⟩, (∆B)2 = ⟨(B̂ − ⟨B̂⟩)2 ⟩.

Using the Cauchy–Schwarz inequality, one can show the general uncertainty relation

1
∆A ∆B ≥ 2
⟨[Â, B̂]⟩ .

A famous example is position and momentum:

ℏ
[x, p] = iℏ ⇒ ∆x ∆p ≥ .
2
This means that no quantum state can have both position and momentum precisely
defined.
The uncertainty principle is not a statement about experimental imperfec-
tions, but a fundamental property of quantum states.

General Properties of Commutators

Some useful properties of commutators are:

• Antisymmetry: [A, B] = −[B, A].

• Linearity: [A, B + C] = [A, B] + [A, C].

• Scalar multiplication: [A, λB] = λ[A, B] for any number λ.

• [AB, C] = A[B, C] + [A, C]B.

• [A, BC] = B[A, C] + [A, B]C.

• Jacobi identity: [A, [B, C]] + [B, [C, A]] + [C, [A, B]] = 0.

• If [A, B] = 0, then the eigenvectors of A are also the eigenvectors of B.

Physical Implications
• Non-commuting observables cannot have simultaneous sharp values.

• Measurement of one observable generally prepares the system in an eigenstate that

is not an eigenstate of the other.

• The uncertainty principle is a mathematical consequence of non-commutativity.

• Compatible observables (commuting operators) can be measured simultaneously

without disturbance.

Note that quantum mechanics is not merely probabilistic because of exper-

imental limitations; rather, the probabilistic nature is intrinsic to the theory
itself.
18 MODULE 3. POSTULATES OF QUANTUM MECHANICS

Question :

Show that
[x̂, p̂x ] = iℏ.

Solution :

In the position representation, the momentum operator is given by

∂
p̂x = −iℏ .
∂x

Let ψ(x) be an arbitrary wavefunction. Then,

[x̂, p̂x ]ψ(x) = (x̂p̂x − p̂x x̂)ψ(x).

Compute each term:

 
dψ dψ
x̂p̂x ψ = x −iℏ = −iℏ x ,
dx dx
 
d dψ
p̂x x̂ψ = −iℏ (xψ) = −iℏ ψ + x .
dx dx
Subtracting,
 
dψ dψ
[x̂, p̂x ]ψ = −iℏ x + iℏ ψ + x = iℏ ψ.
dx dx
Since this holds for any ψ(x),
[x̂, p̂x ] = iℏ.

Note

One can similarly show that

[x̂, p̂y ] = [x̂, p̂z ] = 0, [x̂, ŷ] = [x̂, ẑ] = [ŷ, ẑ] = 0, [p̂x , p̂y ] = [p̂y , p̂z ] = [p̂z , p̂x ] = 0.

In general, the canonical commutation relations can be written compactly as

[x̂i , p̂j ] = iℏ δij , [x̂i , x̂j ] = [p̂i , p̂j ] = 0,

where i, j ∈ {1, 2, 3}, with

x̂1 = x̂, x̂2 = ŷ, x̂3 = ẑ.

Similarly,
p̂1 = p̂x , p̂2 = p̂y , p̂3 = p̂z .
3.6. TIME EVOLUTION 19

3.6 Time Evolution

In classical mechanics, the future motion of a particle is determined by its initial position
and velocity. Quantum mechanics, however, replaces deterministic trajectories with the
evolution of probability amplitudes.

Postulate 5 (Time Evolution): The time evolution of a quantum state is gov-

erned by the Schrödinger equation.

Although we previously encountered the Schrödinger equation when studying matter

waves, we now elevate it to the status of a fundamental law of nature. It is not derived
from deeper principles within non-relativistic quantum mechanics; its validity rests on
experimental success.

3.6.1 Time-Dependent Schrödinger Equation

The fundamental dynamical law of non-relativistic quantum mechanics is the time-dependent
Schrödinger equation (TDSE):

∂
iℏ Ψ(r, t) = ĤΨ(r, t),
∂t

where Ψ(r, t) is the wave function and Ĥ is the Hamiltonian operator representing the
total energy of the system.
For a single particle in one dimension,

ℏ2 ∂ 2
 
∂
iℏ Ψ(x, t) = − + V (x, t) Ψ(x, t).
∂t 2m ∂x2

3.6.2 Time-Independent Schrödinger Equation

When the Hamiltonian does not depend explicitly on time, the Schrödinger equation
admits a special class of solutions that play a central role in quantum mechanics. These
solutions allow the problem of time evolution to be reduced to an eigenvalue equation.
We start from the time-dependent Schrödinger equation (TDSE) for a single particle
in one space dimension:

ℏ2 ∂ 2
 
∂
iℏ Ψ(x, t) = Ĥ Ψ(x, t) = − + V (x, t) Ψ(x, t).
∂t 2m ∂x2

Separation of variables: derivation

If the potential is independent of time, V (x, t) = V (x), we attempt a separable solution
of the form
Ψ(x, t) = ψ(x) ϕ(t),
where ψ depends only on x and ϕ depends only on t. Substituting into the TDSE gives

ℏ2 d2 ψ(x)
 
dϕ(t)
iℏ ψ(x) = − + V (x) ψ(x) ϕ(t).
dt 2m dx2
20 MODULE 3. POSTULATES OF QUANTUM MECHANICS

Divide both sides by ψ(x) ϕ(t) to separate variables:

1 dϕ(t) ℏ2 1 d2 ψ(x)
iℏ =− + V (x).
ϕ(t) dt 2m ψ(x) dx2
The left-hand side is a function of t only and the right-hand side is a function of x only.
The only way a function of t can equal a function of x for all x and t is if both sides are
equal to the same constant. We call that separation constant E. Thus we obtain two
ordinary differential equations:
1 dϕ dϕ iE
iℏ =E ⇒ = − ϕ,
ϕ dt dt ℏ
whose solution is
ϕ(t) = e−iEt/ℏ
and
ℏ2 d2 ψ(x)
− + V (x)ψ(x) = E ψ(x).
2m dx2
The last equation is the time-independent Schrödinger equation (TISE)
ℏ2 d2
Ĥψ(x) = Eψ(x), Ĥ ≡ − + V (x).
2m dx2

Reality of the separation constant E

Assume ψ(x) is normalizable and satisfies appropriate boundary conditions (for example
ψ(x) → 0 as |x| → ∞). Multiply the TISE by ψ ∗ (x) and integrate over all space:
Z ∞ Z ∞ Z ∞
∗ ∗
ψ (x) Ĥ ψ(x) dx = ψ (x) E ψ(x) dx = E |ψ(x)|2 dx.
−∞ −∞ −∞

The Hamiltonian Ĥ is a Hermitian operator for real potentials underR the stated boundary
conditions, so the left-hand side is real. If we normalize ψ so that |ψ|2 dx = 1, then
Z
E = ψ ∗ Ĥψ dx ∈ R.

Hence the separation constant E must be real. Equivalently one can take the complex
conjugate of the TISE and use the Hermiticity of Ĥ to reach the same conclusion.

Stationary states and their properties

A separable solution gives the full time-dependent wave function

Ψ(x, t) = ψ(x) e−iEt/ℏ .

Although Ψ(x, t) depends on time, the probability density is time independent:

|Ψ(x, t)|2 = ψ ∗ (x)ψ(x) = |ψ(x)|2 ,

because the time factor cancels. Such solutions are called stationary states. In particular
every expectation value of an operator that does not depend explicitly on time is constant
in time for a stationary state.
3.6. TIME EVOLUTION 21

The expectation value of the energy in the stationary state is exactly E:

Z Z Z
∗ ∗
⟨H⟩ = Ψ (x, t) Ĥ Ψ(x, t) dx = ψ (x) Ĥ ψ(x) dx = E |ψ|2 dx = E,

again assuming normalized ψ. The variance of the energy is zero:

2
σH = ⟨H 2 ⟩ − ⟨H⟩2 = E 2 − E 2 = 0,

so an energy measurement always returns the value E with certainty in a stationary state.

Thus, stationary states are energy eigenstates and represent quantum ana-
logues of classical states with definite energy.

Remarks
• The separation method works only when V does not depend on time. If V = V (x, t)
the TDSE must be solved directly.

• Solving the TISE for a particular potential V (x) (for example the infinite square
well, harmonic oscillator, or potential step) yields the energies En and eigenfunctions
ψn (x). These form the building blocks for the full time evolution of any initial state.

Solving the time-independent Schrödinger equation is one of the central tasks of

quantum mechanics. Once its eigenvalues and eigenfunctions are known, the full
time evolution of the system can be constructed.

We will see some examples in the next module.

Problems
Problem 1

Consider a quantum system defined by a two-dimensional Hilbert space with orthonormal

basis vectors    
1 0
|0⟩ = , |1⟩ = .
0 1
If the system is in the state
1
|ψ⟩ = √ (|0⟩ + |1⟩),
2
what is the expectation value of the observable
 
1 0
 = ?
0 −1
22 MODULE 3. POSTULATES OF QUANTUM MECHANICS

Problem 2
Three dynamical variables of the system, X, Y, Z, are represented by the 2 × 2 matrices
denoted by σx , σy , σz , where
     
0 1 0 −i 1 0
σx = , σy = , σz = .
1 0 i 0 0 −1
Give two different vectors which correspond to a definite value 5 of the dynamical variable
3X + 4Z.

Problem 3
Find a relation between A and B which is necessary so that the following two wave func-
tions may represent the same quantum state:

(a) ψ1 (x) = A cos(kx) + B sin(kx) (b)ψ2 (x) = 2eikx − e−ikx

Problem 4
If the state of a quantum system is given by
|ψ⟩ = 3 |E1 ⟩ + 4i |E2 ⟩ ,
where |E1 ⟩ and |E2 ⟩ are energy eigenstates of the Hamiltonian Ĥ with corresponding
eigenvalues E1 and E2 , what is the average value of the energy in the state |ψ⟩?

Problem 5
Let the probability density for a particle in one dimension be given by ρ(x) = Ae−2|x| .
Normalize the distribution and compute the expectation values ⟨x⟩ and ⟨x2 ⟩.

Problem 6
State the Heisenberg uncertainty principle. Consider a particle in a state with ∆x =
0.1 nm. What is the minimum possible uncertainty in momentum ∆p? Comment on the
implication of this result for the measurement of position and momentum.

Problem 7
In a sequential Stern–Gerlach experiment, atoms initially pass through a Stern–Gerlach
apparatus aligned along the z-axis and are found to be in the spin-up state |+⟩z . These
atoms then pass through a second apparatus aligned along the x-axis. What are the
possible outcomes and their probabilities in this second measurement?

Problem 8
2π
Consider a wave function given by ψ(x) = A sin(kx), where k = λ
and A is a real
constant.
(a) For what values of x is there the highest probability of finding the particle described
by this wave function? Explain.
(b) For which values of x is the probability zero? Explain.
3.6. TIME EVOLUTION 23

Problem 9
An electron is moving as a free particle in the x - direction with momentum of magnitude

p = 4.50 × 10−24 kg · m/s.

What is the one-dimensional time-dependent wave function of the electron?

Problem 10
The wave function
Ψ(x, t) = Aei(k1 x−ω1 t) + Aei(k2 x−ω2 t)
is a superposition of two free-particle wave functions. Both k1 and k2 are positive.

(a) Show that this wave function satisfies the Schrödinger equation for a free particle
of mass m.

(b) Find the probability distribution function |Ψ(x, t)|2 .

Solutions
Problem 1
     
1 0 1 1 1
|0⟩ = , |1⟩ = , |ψ⟩ = √ (|0⟩ + |1⟩) = √
0 1 2 2 1

1
⟨ψ| = (|ψ⟩)† = √ 1 1


2
     
1 0 1 1 1 1
 |ψ⟩ = ·√ =√
0 −1 2 1 2 −1
 
1
1 1
⟨ψ| Â |ψ⟩ = 1 1 = (1 − 1) = 0
2 −1 2

Answer: ⟨Â⟩ = 0

Problem 2
     
0 1 1 0 4 3
Let A = 3X + 4Z = 3σx + 4σz = 3 +4 =
1 0 0 −1 3 −4

4−λ 3
Find eigenvalues by solving det(A − λI) = 0 : =0
3 −4 − λ

(4 − λ)(−4 − λ) − 9 = λ2 − 16 − 9 = λ2 − 25 = 0 ⇒ λ = ±5

For λ = 5 : (A − 5I)⃗v = 0
24 MODULE 3. POSTULATES OF QUANTUM MECHANICS

  
−1 3 v1
⇒ = 0 ⇒ v1 = 3v2
3 −9 v2
 
3
⇒ ⃗v1 = (any multiple is valid)
1
   
3
Answer: λ : λ∈C
1

Problem 3

eikx + e−ikx eikx − e−ikx

ψ1 (x) = A cos(kx) + B sin(kx) = A · +B·
2 2i
   
A B A B
= − ikx
e + + e−ikx
2 2i 2 2i

ψ2 (x) = 2eikx − e−ikx

To represent the same quantum state: ψ1 (x) = C · ψ2 (x), for some complex C

(
A B
2
− 2i
= 2C
⇒ A B
2
+ 2i
= −C

B
Add: A = C, Subtract: = 3C ⇒ B = 3iC
i

Answer: A = C, B = 3iC ⇒ B = 3iA

Problem 4

|ψ⟩ = 3 |E1 ⟩ + 4i |E2 ⟩

⟨ψ |ψ⟩ = |3|2 + |4i|2 = 9 + 16 = 25

1
⇒ normalized state: |ϕ⟩ = (3 |E1 ⟩ + 4i |E2 ⟩)
5
 2
1 1
⟨E⟩ = ⟨ϕ| Ĥ |ϕ⟩ = (9E1 + 16E2 ) = (9E1 + 16E2 )
5 25

9E1 + 16E2
Answer: ⟨E⟩ =
25
3.6. TIME EVOLUTION 25

Problem 5

ρ(x) = Ae−2|x| (even function)

∞ ∞ ∞
e−2x
Z Z 
−2x 1
ρ(x) dx = 2 Ae dx = 2A · = 2A · =A
−∞ 0 −2 0 2

Normalization: A = 1
Z ∞
⟨x⟩ = xρ(x)dx = 0 (odd function over symmetric limits)
−∞
Z ∞
1
2
⟨x ⟩ = 2 x2 e−2x dx = (using integration by parts)
0 2

1
Answers: A = 1, ⟨x⟩ = 0, ⟨x2 ⟩ =
2

Problem 6
ℏ
Heisenberg uncertainty principle: ∆x · ∆p ≥
2
h
∆x = 0.1 nm = 1.0 × 10−10 m, ℏ= ≈ 1.055 × 10−34 J · s
2π
ℏ 1.055 × 10−34
∆p ≥ = = 5.28 × 10−25 kg · m/s
2∆x 2 × 1.0 × 10−10

Answer: ∆p ≥ 5.28 × 10−25 kg · m/s

Interpretation: The more precisely position is known, the less precisely momentum
can be known. High precision in x ⇒ large uncertainty in p.

Problem 7
Atoms are initially in the state  
1
|+⟩z =
0
Spin eigenstates along x-axis are (eigenvectors of σ2x ):
   
1 1 1 1
|+⟩x = √ , |−⟩x = √
2 1 2 −1
Compute inner products:
1 1
⟨+x |+z ⟩ = √ , ⟨−x |+z ⟩ = √
2 2
Probabilities:
1
P (+x ) = |⟨+x |+z ⟩|2 =
2
26 MODULE 3. POSTULATES OF QUANTUM MECHANICS

1
P (−x ) = |⟨−x |+z ⟩|2 =
2
1 1
Answer: Possible outcomes: |+⟩x , |−⟩x Probabilities: ,
2 2

Problem 8

ψ(x) = A sin(kx), ρ(x) = |ψ(x)|2 = A2 sin2 (kx)

(a) Maximum probability occurs when sin2 (kx) = 1:

π (2n + 1)π
sin(kx) = ±1 ⇒ kx = + nπ ⇒ x = , n∈Z
2 2k

(2n + 1)π
Answer (a): x=
2k
(b) Probability is zero when sin(kx) = 0:
nπ
kx = nπ ⇒ x = , n∈Z
k

nπ
Answer (b): x=
k

Problem 9

p = 4.50 × 10−24 kg · m/s, free particle: ψ(x, t) = Aei(px−Et)/ℏ

p2
Energy: E = , Use: ℏ ≈ 1.055 × 10−34 J · s
2m
General form:

p E
ψ(x, t) = Aei(kx−ωt) , k= , ω=
ℏ ℏ

p 4.50 × 10−24
k= = −34
≈ 4.27 × 1010 m−1
ℏ 1.055 × 10

p2 (4.50 × 10−24 )2
E= = −31
≈ 1.11 × 10−17 J
2m 2 × 9.11 × 10

E 1.11 × 10−17
ω= = ≈ 1.05 × 1017 rad/s
ℏ 1.055 × 10−34

Answer: ψ(x, t) = Aei(kx−ωt) with k ≈ 4.27 × 1010 , ω ≈ 1.05 × 1017

3.6. TIME EVOLUTION 27

Problem 10

Ψ(x, t) = Aei(k1 x−ω1 t) + Aei(k2 x−ω2 t)

(a) Show it satisfies the Schrödinger equation:

∂Ψ
iℏ = iℏA(−iω1 )ei(k1 x−ω1 t) + iℏA(−iω2 )ei(k2 x−ω2 t) = ℏω1 Aei(k1 x−ω1 t) + ℏω2 Aei(k2 x−ω2 t)
∂t

ℏ2 ∂ 2 Ψ ℏ2 2 i(k1 x−ω1 t) ℏ2 2 i(k2 x−ω2 t) ℏ2 k12 i(k1 x−ω1 t) ℏ2 k22 i(k2 x−ω2 t)
− = − A(ik 1 ) e − A(ik 2 ) e = Ae + Ae
2m ∂x2 2m 2m 2m 2m

ℏki2
Since ωi = , both sides match ⇒ Schrödinger equation is satisfied
2m
(b) Probability distribution:

|Ψ(x, t)|2 = Ψ∗ (x, t)Ψ(x, t) = Ae−i(k1 x−ω1 t) + Ae−i(k2 x−ω2 t) Aei(k1 x−ω1 t) + Aei(k2 x−ω2 t)
  

= A2 2 + ei((k1 −k2 )x−(ω1 −ω2 )t) + e−i((k1 −k2 )x−(ω1 −ω2 )t)
 

 
2 2 2 (k1 − k2 )x − (ω1 − ω2 )t
= A [2 + 2 cos ((k1 − k2 )x − (ω1 − ω2 )t)] = 4A cos
2
 
2 2 2 (k1 − k2 )x − (ω1 − ω2 )t
Answer: |Ψ(x, t)| = 4A cos
2