PH 112: Introduction to Quantum Physics

Schrodinger Equation and properties of wave

Function
Sunita.srivsatava@phy.iitb.ac.in
Lecture 06: 18-05-2023

Sunita Srivastava
Ext. : 7572
Email : Sunita.srivastava@iitb.ac.in
Learning Objectives

• Classical vs quantum systems.

• Newton’s Equation of motion and Wave equation.

• Introduction to “The Schrödinger Equation”.

Measurement on a classical vs quantum “object”

In classical mechanics, the future of a particle is completely

determined by its initial position and momentum (together with the
forces that act upon it. )

In QM, we arrive at relationships between observable quantities, but

the uncertainty principle suggests that the nature of an observable
quantity is different in the atomic scale.

For example in classical picture the radius of the electron’s orbit in a

ground – state hydrogen atom is always exactly 5.3𝑋10−11 m,
however quantum mechanics states that this is the “most probable
radius “
From Newtonian (Classical) to New (Quantum) world

• Firstly, because the “object” is not a particle in the Newtonian

sense. It is not a wave either.

• Is the wave packet the “object” ?

• NO: It is a function which carries the information about the “state”

of the object.

• And that too…not in a deterministic way but in a probabilistic

way (due to Heisenberg uncertainty principle).
From Newtonian (Classical) to New (Quantum) world

In case of classical waves, we know :

For EM waves, the mutually perpendicular electric and magnetic
fields are oscillating.
In case of elastic waves in a stretched string, one (or two) of the
spatial co-ordinates is(are) oscillating.

Now that we have associated a wave packet with subatomic particle.

Lets ask again “what is oscillating in a de-Broglie wave ?

Probability Amplitude
Born Interpretation
From Classical to Quantum world
Classical Motion vs motion in atomic systems

• In classical world, macroscopic objects are described as particles.

The “state” of particle ( in simple words, position, momentum) is
exactly known.

• HOW ?

• If we know the forces acting on the particle, Newton’s second law

allows us to find the state of a particle at some time t, provided the
state is specified at some other time t’.

• Newton’s second law !!

Newton’s second law
• Mathematically, it is a second order differential equation in time,
with spatial coordinates as dependent variables:

𝑑2 𝑟Ԧ
𝐹Ԧ = 𝑚𝑎 = 𝑚 2
𝑑𝑡
This is the dynamical equation governing the evolution of the
state of a classical particle

𝑑 𝑟Ԧ
So, if 𝑟Ԧ (position) and (velocity) are given for 𝑡 = 𝑡, we can find
𝑑𝑡
𝑑 𝑟Ԧ
the trajectory (𝑟(𝑡))
Ԧ and the state (𝑟,
Ԧ ) at another time 𝑡 = 𝑡′.
𝑑𝑡
Equation to find “state” of matter wave
Ψ 𝑥, 𝑡 provide an information (though probabilistic) about
the position (state, in general) of the particle.
Can we construct an equivalent of Newton’s second law : i.e.
a dynamical equation governing the evolution of the state of
the object ?
We know for classical object;
𝑑2 𝑟Ԧ
𝐹Ԧ = 𝑚 2
𝑑𝑡

BUT, it does not imply any wave-like solution at all !!

Now what ? How about classical wave equation ? LETS
SEE !!
Wave Equation
The equation governing classical wave dynamics

𝜕2𝜑 1 𝜕2𝜑
2
= 2 2
𝜕𝑥 𝑐 𝜕𝑡
Possible solution are
𝜑 𝑥, 𝑡 = 𝐴 cos(𝑘𝑥 − 𝜔𝑡)

𝜑 𝑥, 𝑡 = 𝐴 sin(𝑘𝑥 − 𝜔𝑡)

𝜑 𝑥, 𝑡 = 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡)

𝜑 𝑥, 𝑡 = 𝐴𝑒 −𝑖(𝑘𝑥−𝜔𝑡)
Solutions of this equation must superimpose.
Solutions of the wave Equation
Considering superposition property of waves, if 𝜑1 𝑥, 𝑡 and 𝜑2 𝑥, 𝑡 are solutions
of the eqn.

𝜕2𝜑 1 𝜕2𝜑
=
𝜕𝑥 2 𝑐 2 𝜕𝑡 2
then
𝜑 𝑥, 𝑡 = 𝑎𝜑1 𝑥, 𝑡 +𝑏𝜑2 𝑥, 𝑡

must also be a solution. Lets verify:

𝜕 2 𝜑 𝜕 2 (𝑎𝜑1 + 𝑏𝜑2 ) 𝜕 2 𝜑1 𝜕 2 𝜑2
= =𝑎 +𝑏
𝜕𝑥 2 𝜕𝑥 2 𝜕𝑥 2 𝜕𝑥 2
1 𝜕 2 𝜑1 1 𝜕 2 𝜑2
=𝑎 2 +𝑏 2
𝑐 𝜕𝑡 2 𝑐 𝜕𝑡 2
Wave Equation
Since 𝜑1 and 𝜑2 are solutions of the wave equation.

𝜕2𝜑 1 𝜕 2 (𝑎𝜑1 + 𝑏𝜑2 ) 1 𝜕2𝜑

2
= 2 2
= 2 2
𝜕𝑥 𝑐 𝜕𝑡 𝑐 𝜕𝑡

We see that 𝑎𝜑1 + 𝑏𝜑2 is also a solution of the wave equation. But
note that here 𝒄 is same for both the waves.

𝜑 would not be a solution of the wave equation if 𝜑1 and 𝜑2 had

different velocities.
But to form a wave packet, we need waves travelling at different
speeds to superimpose. The dynamical equation should also govern the
evolution of the wave packet.
So, the standard wave equation cannot be used for de Broglie waves.
We need something different .
The Schrödinger Equation
The differential equation whose solution gives us the wave behavior of
particle is called the Schrödinger Equation.

ℏ𝟐 𝝏𝟐 𝜳
− + 𝐕 𝐱 𝜳(x) = E 𝜳(x)
𝟐𝒎 𝝏𝒙𝟐

E is the total energy ; V is the potential energy.

This is the time-independent Schrödinger Equation for 1D motion.

Have you derived Newtons law ?? NO

Newton’s laws of motion were not derived from any other principles.

Lets consider the motion of a free particle and justify the form of the
SE.
The Schrödinger Equation: “Derivation”
Lets consider the motion of a free particle (which is a particle that is
not under the influence of any forces and therefore pursues a straight
path at constant speed) to be given by
Ψ 𝑥 = 𝐴 𝑆𝑖𝑛𝑘𝑥
2π
A is the amplitude of the wave and k is the wave number =
λ
𝜕Ψ
Differentiating Ψ 𝑥, 𝑡 w.r.t. to 𝑥 = 𝑘𝐴𝐶𝑜𝑠𝑘𝑥
𝜕𝑥

𝜕2 Ψ
Differentiating Ψ 𝑥, 𝑡 twice w.r.t. to 𝑥 = −𝑘 2 Ψ
𝜕𝑥 2

𝑝2 ℏ2 𝑘 2
Since Kinetic energy, K = =
2𝑚 2𝑚

𝜕2 Ψ 2𝑚𝐾
= −𝑘 2 Ψ 𝑥 = − 2 Ψ(𝑥)
𝜕𝑥 2 ℏ
The Schrödinger Equation: “Derivation”
𝜕2 Ψ 2𝑚𝐾
=− Ψ(𝑥)
𝜕𝑥 2 ℏ2
𝜕2 Ψ 2𝑚(𝐸−𝑉)
=− Ψ(𝑥)
𝜕𝑥 2 ℏ2
E = V+K is the nonrelativistic total energy of the particle.
V is the potential energy.
ℏ2 𝜕 2 Ψ
For a free particle, V=0 so E=K − = 𝐸 Ψ(𝑥)
2𝑚 𝜕𝑥 2

ℏ𝟐 𝝏𝟐 𝜳
− + 𝐕 𝐱 𝜳(x) = E 𝜳(x)
𝟐𝒎 𝝏𝒙𝟐

The time independent Schrodinger equation is a wave equation in

terms of the wavefunction which plays the same role as of Newton's
laws and conservation of energy in classical mechanics - i.e., it
predicts the future behavior of a dynamic system.
The time dependent Schrödinger Equation
The time dependent SE in differential form is,
𝝏𝜳(𝒙, 𝒕) ℏ𝟐 𝝏𝟐 𝜳(𝒙, 𝒕)
𝒊ℏ =−
𝝏𝒕 𝟐𝒎 𝝏𝒙𝟐
Let one of the component waves of the wave packet representing a free
particle (which is a particle that is not under the influence of any forces
and therefore pursues a straight path at constant speed.) to be given by

Ψ 𝑥, 𝑡 = 𝑒 𝑖(𝑘𝑥−𝜔𝑡)
𝐸
where 𝜔 = E is Electron energy
ℏ
𝑝
and 𝑘 = (p is electron momentum)
ℏ

𝜕Ψ
Differentiating Ψ 𝑥, 𝑡 once w.r.t. to 𝑡 = −𝑖𝜔Ψ
𝜕𝑡

𝜕2 Ψ
Differentiating Ψ 𝑥, 𝑡 twice w.r.t. to 𝑥 = −𝑘 2 Ψ
𝜕𝑥 2
The Schrödinger Equation: “Derivation”
𝜕Ψ 𝜕2Ψ 2Ψ
= −𝑖𝜔Ψ = −𝑘
𝜕𝑡 𝜕𝑥 2
𝜕Ψ ℏ2 𝜕2 Ψ ℏ2 k2
𝑖ℏ = ℏ𝜔Ψ = 𝐸Ψ − = Ψ
2m 𝜕x2 2m
𝜕𝑡

For a free particle,

ℏ2 𝑘 2
=
𝑝2
= 𝐸; ℏ2 𝜕 2 Ψ
2𝑚 2𝑚 − = 𝐸Ψ
2𝑚 𝜕𝑥 2

Thus, we can write 𝜕Ψ ℏ2 𝜕 2 Ψ

𝑖ℏ =−
𝜕𝑡 2𝑚 𝜕𝑥 2
The is the time dependent Schrödinger Equation.

Note that the equation is free from parameters of the motion of particle or the
associated wave.
Wave Packet and the Schrödinger Equation: “Derivation”

The time dependent Schrödinger Equation. 𝜕Ψ ℏ2 𝜕 2 Ψ

𝑖ℏ =−
𝜕𝑡 2𝑚 𝜕𝑥 2

The solution will be satisfied by a wave function of the form Ψ 𝑥, 𝑡 = 𝑒 𝑖(𝑘𝑥−𝜔𝑡)

But Ψ 𝑥, 𝑡 = 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡) is a wave of infinite extent.

For the equation to govern the evolution of the QM particle, we rather need a
wave-packet, constructed out of linear superposition of these “plane waves”
to satisfy it. So, we consider
Ψ 𝑥, 𝑡 = න 𝐴(𝑘)𝑒 𝑖(𝑘𝑥−𝜔(𝑘)𝑡) 𝑑𝑘
Wave Packet and the Schrödinger Equation: “Derivation”

𝜕Ψ 𝜕
𝑖ℏ = 𝑖ℏ න 𝐴(𝑘)𝑒 𝑖(𝑘𝑥−𝜔(𝑘)𝑡) 𝑑𝑘
𝜕𝑡 𝜕𝑡

= න ℏ𝜔(𝑘) 𝐴 𝑘 𝑒 𝑖 𝑘𝑥−𝜔 𝑘 𝑡
𝑑𝑘

ℏ2 𝑘 2
=න 𝐴 𝑘 𝑒𝑖 𝑘𝑥−𝜔 𝑘 𝑡
𝑑𝑘
2𝑚

ℏ2 𝜕 2
=− 2
න 𝐴 𝑘 𝑒𝑖 𝑘𝑥−𝜔 𝑘 𝑡 𝑑𝑘
2𝑚 𝜕𝑥

𝜕Ψ ℏ2 𝜕 2 Ψ Time dependent
𝑖ℏ =−
𝜕𝑡 2𝑚 𝜕𝑥 2 Schrödinger Equation

The wave packet does satisfy the equation

The Schrödinger Equation
𝜕Ψ(𝑥,𝑡) ℏ2 𝜕2 Ψ 𝑥,𝑡
So, we can write, 𝑖ℏ = − + 𝑉Ψ(𝑥, 𝑡)
𝜕𝑡 2𝑚 𝜕𝑥 2

This is the one-dimensional Time-Dependent Schrodinger Equation

(TDSE).

In 3 dimensions, TDSE is written as

𝜕Ψ ℏ2 2
𝑖ℏ =− 𝛻 Ψ + 𝑉Ψ
𝜕𝑡 2𝑚

Time-Dependent Schrodinger Equation in 3D.

Properties of Ψ(x,t)
• Ψ is wave function and is a function of (x,t). In general Ψ≡ Ψ(𝑥, 𝑡) (1D).

• It contains all information about the physical properties of the particle.

• Ψ is not a physically measureable quantity
• The probability of finding the particle between x and x+dx at time t is given by
│ 𝜳 │2 dx.

• SE is linear in 𝛹. It implies if 𝛹1 and 𝛹2 are two solutions of SE, then

𝜑 = 𝑎Ψ1 +𝑏Ψ2 is also a solution.
• Wave functions add but NOT probabilities

𝑃1 = │ Ψ1 │2
𝑃2 = │ Ψ2 │2
𝛹 = Ψ1 +Ψ2
𝑃 ≠ 𝑃1 + 𝑃2
Properties of the Wave function 𝚿 𝐱, 𝐭
𝒃
Normalization: We discussed earlier that ‫𝒙 𝜳 𝒂׬‬, 𝒕 𝟐 𝒅𝒙, is the
probability of finding the particle between 𝑎 and 𝑏 at time 𝑡.

Since, the total probability of finding the particle in all space should be
one. In 1D, ∞
න Ψ 𝑥, 𝑡 2 𝑑𝑥 =1
−∞

∞
In 3D, න Ψ 𝒓, 𝑡 2 3
𝑑 𝑟=1
−∞

Where 𝑑3 𝑟 = 𝑑𝑥𝑑𝑦𝑑𝑧 , or 𝑑 3 𝑟 = 𝑟 2 sin 𝜃 𝑑𝑟𝑑𝜃𝑑ϕ

Probability Density, P(x) and Normalization of 𝜳 𝒙
Ψ 𝑥 2 is product of complex conjugate with itself and represents the
intensity of the matter wave and
𝑃 𝑥 = Ψ 𝑥 2 = Ψ 𝑥 *Ψ 𝑥
P x is the probability density (per unit length).

Note Ψ 𝑥 itself is not a measurable quantity P(x) is measureable and tells us

about the probability for finding the particle at the point x at time t.

Since tℎ𝑒 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑚𝑢𝑠𝑡 𝑏𝑒 𝑓𝑜𝑢𝑛𝑑 𝑠𝑜𝑚𝑒𝑤ℎ𝑒𝑟𝑒 𝑎𝑙𝑜𝑛𝑔 𝑡ℎ𝑒 𝑥 −

𝑎𝑥𝑖𝑠 1𝐷 , 𝑡ℎ𝑒 probabilities summed over all values of x must be = 1

∞
න Ψ 𝑥 2 𝑑𝑥 =1 Ψ 𝑥 is normalized
−∞
Normalization of the wave function (Ex:1)
Let us look at an example: Lets say that we are given a wave function
𝑚𝑥 2
Ψ 𝑥, 𝑡 = 𝐴𝑒 −𝑎( ℏ +𝑖𝑡)
where 𝐴 and 𝑎 are positive real constants

Lets normalize the wave function: In other words, lets find 𝐴 such that
∞
2
න Ψ 𝑥, 𝑡 𝑑𝑥 = 1
−∞

∞ 𝑚𝑥 2 𝑚𝑥 2
න 𝐴𝑒 −𝑎( ℏ +𝑖𝑡) 𝐴𝑒 −𝑎( ℏ −𝑖𝑡) 𝑑𝑥 =1
−∞

2
2 ∞ −2𝑎𝑚𝑥 𝜋ℏ
𝐴 ‫׬‬−∞ 𝑒 ℏ 𝑑𝑥 = 1 𝐴2 =1
2𝑚𝑎

1Τ4
2𝑚𝑎 𝑚𝑥 2
−𝑎( ℏ +𝑖𝑡)
So Ψ 𝑥, 𝑡 = 𝑒
𝜋ℏ
Normalization of the wave function (Ex:2)

If we consider a “free” wave, i.e. Ψ 𝑥, 𝑡 = 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡)

it is immediately seen that

∞ 2
‫׬‬−∞ Ψ 𝑥, 𝑡 𝑑𝑥 = 𝐴∗ 𝐴 𝑒 −𝑖(𝑘𝑥−𝜔𝑡) 𝐴 𝑒 𝑖(𝑘𝑥−𝜔𝑡) = 1

∞
𝐴 2 ‫׬‬−∞ 𝑑𝑥 = 1

cannot be normalized.

Ψ 𝑥, 𝑡 , is not square-integrable, and therefore does not represent the state

of a real particle.
Restrictions on the Wavefunction 𝜳 𝒓, 𝒕 , (Well-behaved wave function)

What are the restrictions on Ψ(𝑥, 𝑡) which satisfies the SE ?

∞
1. Normalization.
න 𝜳 𝒙, 𝒕 𝟐 𝒅𝒙 = 𝟏
2. Square integrable. −∞

3. Single-valued.
4. Wavefunction and derivative must be continuous.
Introduction to Observable and operators
Observables: An observable is any particle property that can be
measured. For e.g, the position and momentum of a particle are
observables, as are its kinetic and potential energies.

Operators: An operator is “something” that acts on a function and

converts it to another function.
𝑑
෠
If 𝑂 is an operator , let say derivative operator then 𝑂 =
𝑑𝑥
𝑑
෠
𝑂𝑓(𝑥) = 𝑓 𝑥 ; 𝑖𝑓 𝑓 𝑥 = 𝑆𝑖𝑛 𝑘𝑥
𝑑𝑥
෠ 𝑥 = 𝑘 𝐶𝑜𝑠 𝑘𝑥
𝑂𝑓
In quantum mechanics, we associate an operator with each of the
observables. Using this operator, one can calculate the average value
of the corresponding observable.
 In quantum physics we come across several operators. For every
physical quantity (observable) there is an operator ,
𝜕
Momentum operators (𝑃෠ = −𝑖ℏ )
𝜕𝑥
𝜕
෠
Energy operators (and 𝐸 = 𝑖ℏ )
𝜕𝑡

are examples of differential operators

However, not all operators need to be differential. We can call 𝑋෠ an

operator which multiplies Ψ 𝑥, 𝑡 with 𝑥 to give a new(wave)function.

෠ 𝑥, 𝑡 = 𝜙 𝑥, 𝑡 = 𝑥Ψ 𝑥, 𝑡
i.e. 𝑋Ψ

Measurable parameters in QM are associated with operators (with a

special property)
Eigen Values and Eigen Functions
Consider an operators such that 𝑂෠ such that ;

𝑂෠ Ψ 𝑥, 𝑡 = αΨ 𝑥, 𝑡
𝑂෠ 𝑖𝑠 𝑎𝑛 𝒐𝒑𝒆𝒓𝒂𝒕𝒐𝒓, 𝑜𝑝𝑒𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑛 Ψ 𝑥, 𝑡 gives back Ψ 𝑥, 𝑡 .
• Ψ 𝑥, 𝑡 is an eigen function for operator 𝑂෠ .
• α is an eigen value.
Examples:
𝑑 𝑑
𝑂෠ = 𝑓 𝑥 = 𝑒 α𝑥 ෠
𝑂f(x)= 𝑒 α𝑥 = αf(x)
𝑑𝑥 𝑑𝑥
𝑑
෠
𝑂=x 𝑓 𝑥 = 𝑎𝑥 𝑛 ෠
𝑂f(x)= nf(x)
𝑑𝑥
𝑑 ෠
𝑂෠ = 𝑓 𝑥 = 𝑠𝑖𝑛𝑘𝑥 𝑂f(x)≠ nf(x)
𝑑𝑥
f(x) is not an eigenfunction of A
Momentum and Energy Operators

We note that for Ψ 𝑥, 𝑡 = 𝐴𝑒 𝑖 𝑘𝑥−𝜔𝑡

𝜕
𝑃෠ Ψ 𝑥, 𝑡 = −𝑖ℏ Ψ 𝑥, 𝑡 = ℏ𝑘𝐴𝑒 𝑖 𝑘𝑥−𝜔𝑡
= ℏ𝑘Ψ 𝑥, 𝑡 = 𝑝Ψ 𝑥, 𝑡
𝜕𝑥

and
𝜕
෠ 𝑥, 𝑡 = 𝑖ℏ
𝐸Ψ Ψ 𝑥, 𝑡 = ℏ𝜔𝐴𝑒 𝑖 𝑘𝑥−𝜔𝑡 = ℏ𝜔Ψ 𝑥, 𝑡 = 𝐸Ψ 𝑥, 𝑡
𝜕𝑡
Schrödinger Equation in Operator Language
𝜕Ψ ℏ2 𝜕 2 Ψ
𝑖ℏ =−
𝜕𝑡 2𝑚 𝜕𝑥 2

1 𝜕 𝜕
෠ =
𝑖. 𝑒. 𝐸Ψ −𝑖ℏ −𝑖ℏ Ψ
2𝑚 𝜕𝑥 𝜕𝑥
or
𝑃෠ 2
෠
Ψ = 𝐸Ψ
2𝑚

This is the dynamical equation governing the evolution of a free

particle, i.e. particle not subject to any external force.
Wave function and expectation values
If we make measurements of a dynamical variable (energy, momentum,
position) on a large number of identical particles with the same wave function,
we can talk of a expected (average) value of the variable.
Expectation value is the average value of an operator (O) that one would get
after a very large number of measurements are made on identical systems.
The operator is sandwiched between Ψ ∗ and Ψ and integrated over the whole
space.
The expectation value of 𝑥
∞
𝑋෠ = න Ψ ∗ 𝑋෡ Ψ𝑑𝑥
−∞

where Ψ ∗ is the complex conjugate of Ψ.

This is true, provided Ψ is normalized. Otherwise,

∞
‫׬‬−∞ Ψ ∗ 𝑋෠ Ψ𝑑𝑥
𝑋෠ = ∞
‫׬‬−∞ Ψ ∗ Ψ𝑑𝑥
Wave function and expectation values
Likewise
∞
𝑋෠ 2 = න Ψ ∗ 𝑥 2 Ψ𝑑𝑥
−∞
provided Ψ is normalized.

If Ψ is not normalized,
∞
‫׬‬−∞ Ψ ∗ 𝑥 2 Ψ𝑑𝑥
𝑋෠ 2 = ∞
‫׬‬−∞ Ψ ∗ Ψ𝑑𝑥

We can also calculate the expectation values of energy, momentum

etc., but now we need to make use of the corresponding operators.
Wave function and expectation values
The expectation value of energy 𝐸෠

∞ ∞
𝜕
𝐸෠ = න ෠
Ψ ∗ 𝐸Ψ𝑑𝑥 =න Ψ∗ 𝑖ℏ Ψ𝑑𝑥
−∞ −∞ 𝜕𝑡

The expectation value of 𝑃෠

∞ ∞
𝜕
𝑃෠ = න Ψ ∗ 𝑃Ψ𝑑𝑥
෠ =න Ψ ∗
−𝑖ℏ Ψ𝑑𝑥
−∞ −∞ 𝜕𝑥

We could also write,

∞ ∞
𝑋෠ = න Ψ ∗ 𝑋Ψ𝑑𝑥
෠ = න Ψ ∗ 𝑥 𝑥Ψ𝑑𝑥
−∞ −∞

The operator is sandwiched between Ψ ∗ and Ψ and integrated over the

whole space.
Key Points : Wave Functions and Operators
Key Points : Wave Functions and Operators
Recalculating Heisenberg Uncertainty
for Gaussian wave packet using
operator form