Deterministic to Probabilistic World!

At this point we know

Dual character of matter and radiation
 Trajectory can not be defined for a subatomic particle
Uncertainty principle
Quantization concept
Need a new theory to account for these observation?
Quantum theory: Describes the wave character of a particle
How?
By writing wave equations  Second order partial differential
equations (Schrödinger wave equation)

The solution to the Schrödinger wave equation for a system

is the wave function () 1
 WAVEFUNCTION () (PSI)
Classically, the state of a system is described by its position
and momentum
In Quantum theory, the state of a system is described by its
wavefunction

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 WAVEFUNCTION () (PSI)

1. A wavefunction is a mathematical function (like sinx, ex).

Like any mathematical function it can have large value at
some place, small in other and zero elsewhere.
It can be real or complex
2. A wavefunction contains all information about the system
3. The wavefunction is a function of Cartesian coordinate
and time. ie.  (x, y, z, t)

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 THE BORN INTERPRETATION
The state of a system (particle) is
completely specified by its wavefunction 
(x,y,z,t), which is a probability amplitude
and has the significance that
 2 dV or  2 d
(more generally  2dV since  may be
complex)
represents the probability that the particle
is located in the infinitesimal element of
volume dV about the given point, at time t.

Probability density =  2

Probability =  2dV or  2dx (if it is one dimension)
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 NORMALIZATION
As per Born interpretation, the probability of existence of
the particle in the entire space should be 1.
In mathematical term the wave function has to be normalized

For one dimension N 2  2 dx  1

or
N 2  dx  1
Where N is the normalization constant
1
N
 dx
2
1
2
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Restriction on the wavefunction from Born Interpretation

1. From Normalization, has to be bounded or finite

2.  has to be single valued
3.  has to be continuous

To 

  

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Problem 8. Which of the following functions are
acceptable wavefunctions and which are not. State Why

(a ) f ( x)  x 2  1 where x can have any value Not acceptable

Not bounded
(b) f(x)  Sin 1 x, (-1,1) Not acceptable
Multiple values
1 x   acceptable
(c )   sin ,  x 
2 2 2 2
1 Not acceptable
(d )   ,0  x  10  as x4
4-x
1
( e)   ,0  x  3 acceptable
4-x

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8
 Schrödinger Equation
Schrödinger investigated what type of equation de Broglie’s
matter-wave should obeys
The wavefunction  satisfies the Schrödinger equation:

or: Ĥψ=Eψ
where Ĥ is called the Hamiltonian operator, a set of well defined
operations to be carried out on the function ψ, and represents the
energy. In one dimension, the Hamiltonian may be written as
Ĥ=
where V(x) is the potential energy to which the particle is
subjected.
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 Schrodinger equation
In three dimensions,

Ĥψ=Eψ
When ψ is operated upon by Ĥ, returns the ψ multiplied by E

Where H =

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 Schrodinger equation
In spherical polar coordinate we write the Laplacian
operator as

The time dependent Schrodinger

equation is
 Quantum mechanical principles: The
information in a wavefunction
A wavefunction describes the state of a system
How?
The state of a system is described by some measurable
quantities such as mass, volume, momentum, position,
Energy etc. These quantities are called observables

How to determine the observables from wavefunction ()

By performing a set of well defined mathematically
operations on . These mathematical operations are
called operators

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 Eigen value equations
The Schrödinger wave equation, Ĥ ψ = E ψ
Is a category of equation called eigen (=own) value eqn
(operator) (function)= (constant factor) (function)

d ax
dx
   
e ae ax

The Schrödinger wave equation can be written as a

eigen value equation as
(energy operator) ()= (Energy) ()

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Similar equations can be written for other observables like
momentum, dipole moment etc. We can write the corresponding
operators. If the wavefunction is an “eigen function” of the
operator than we can calculate the value of the property

According to quantum mechanical principle

“observable  are represented by operator built from the
following position and momentum operators

Using the above two operators, it is possible to construct operators

for other observables
For example to construct, the kinetic energy operator in one
dimension, we know that

So the corresponding operator is

In mathematics, the second derivative of a function is a measure

of its curvature .
A large second derivative indicates a sharply curved function.
It follows that a sharply curved wavefunction is associated with
high kinetic energy.
A low curvature indicate less kinetic energy.
The curvature of a wavefunction in general
varies from places to places. Wherever, a
wavefunction is sharply curved, its contribution
to the total kinetic energy is large. The
contribution is low if it is less curved.
Suppose for a system the total energy and PE varies
as shown below, then obviously, the wavefunction
becomes more sharp as x increases. So we can
gusess/predict how the wavefunction will look like
wrt different position.
Quantum mechanical operators for different observables
 The information in a wavefunction:
the probability density
Let us consider a free particle (potential energy = 0) of mass
m travelling along the x-axis
For this system we can write the Schrodinger wave equation as

Because V is zero, the equation is

Which can be rearranged

Now,
The equation becomes

Which is rearranged to

The above is a ordinary second order differential equation which is

easy to solve, let

So the two solutions to the equation are

The general solution is a linear combination of two solutions

Where A and B are arbitrary constants. We will
see later how to determine the constants
To verify that the above is a solution of the S.W.E., you can put it back in the
equation and verify
Suppose, in the general solution B = 0, then -------(1)

Where is the particle? We need to find out the probability density

 The probability density is independent of x.

 Where ever we look along x, there is a equal probability
 So if the particle is described by the wavefunction from eq
(1), we can not predict where willl be the particle.
 We get the same case if we take B=0.
 Now consider a second scenario where A= B
-------(2)

The probability density is

A plot of the wavefunction and

probability density is

1. The probability density periodically varies between 0 and 4/A/2.

2. The location at which the probability density is zero is called a
node in the wave function.
“A node is an interior point where the wavefunction passes
through zero”
3. A particle will never be found at the nodal points.
We know now how to use probability density to describe the
location of the particle. Let us extent this discussion to the
momentum of the particle.

If we consider that the equation (2) represent the particle (A =

B case)

The momentum operator is

This equation is not a “Eigen value equation” because the

function on the right is different from left.
When the wavefunction of a particle is not an eigen function of
a operator , the property to which the operator corresponds
does not have a definite value
However, in the present case the momentum is not completely
indefinite, because

And eikx and e-ikx correspond to the definite momentum state

In this case we say that, the wavefunction is a superposition of

more than one wavefunctions.

Linear momentum Linear momentum

of the particle = kħ of the particle =- kħ
The interpretation of the composite function is that

(1) If the momentum of the particle is repeatedly measured ,

then its magnitude of momentum will be found to be kħ in
all measurements.
(2) However, in half of the measurements the particle is
moving towards right (+kħ) and in other half
measurement it will be moving towards left (-kħ).
(3) So we cannot predict, in which direction the particle will
be travelling.
The same interpretation is applied to any wavefunction which is
written as linear combination of eigen functions of a operator.

Where Ck are the coefficients of linear combination and  k are the

eigen functions. Then according to quantum mechanics

1. When the quantity is repeatedly measured, in a single observation

one of the eigen values corresponding to a  k will be found.
2. The probability of measuring a particular eigen value in a series
of observations is proportional to the
3. The average value for a large number of observations is given by
the expectation value of the operator.
 The information in a wavefunction:
The uncertainty principle
We have seen that when the wavefunction is Aeikx, then the
particle it describes has a definite state of momentum kħ and
travelling towards right. However, the position of the particle is
completely unpredictable.

In other words, if the momentum is specified precisely, it is

impossible to specify the location of the particle

So this is half of the uncertainty principle

“It is impossible to specify simultaneously, with arbitrary

precision both the position and momentum of the particle”
The second half is
“If we know the position of the particle exactly, we can say
nothing about its momentum”
From quantum mechanical approach, if we know the position of
the particle, then the wavefunction of the particle will be
extremely large at that point and zero everywhere else.

How do we get such a wavefunction

By superimposing a large number of

harmonic waves of the form eikx

𝝍= 𝑪𝒌 𝝍𝒌 𝒘𝒉𝒆𝒓𝒆 𝒌 𝒊𝒔 𝒗𝒆𝒓𝒚 𝒍𝒂𝒓𝒈𝒆

𝒌
The superposition of a few harmonic waves gives a wavefunction
spreads through a range of location.
However, as the number of harmonic waves increases, the
wavepacket becomes sharper due to complete constructive
interference
When infinite number of components are
used the wavefunction is sharp and
infinitely narrow spike which corresponds
to the perfect localization of the particle.

However, we lost all information about

momentum. Because when we measure
momentum, we will get a value
corresponding to any one of the infinite
number of waves in the superposition.
Thus it becomes unpredictable.
This result is written quantitatively as
ℏ
∆𝑃𝑥 ∆𝑋 ≥
2
The uncertainty principle is applied to any pair of complementary
observables.
In terms of their operators, we say two observables are
complimentary if

𝜴𝟏 𝜴𝟐 𝝍 ≠ 𝜴𝟐 𝜴𝟏 𝝍

When the effect of two operators depends on their order, we say

they do not commute.

Then the commutator of the two operator is defined as

𝜴𝟏 , 𝜴𝟐 = 𝜴𝟏 𝜴𝟐 − 𝜴𝟐 𝜴𝟏
Thus for any pair of observable  1 and  2, the uncertainty in
simultaneous determination is given by
𝟏
∆𝜴𝟏 ∆𝜴𝟐 ≥ [𝜴𝟏 , 𝜴𝟐 ]
𝟐

This is the most general form of the uncertainty principle.