2. Quantum Postulates

Importance of the Hamiltonian Operator
Let 𝜓(𝑥, 𝑦, 𝑧) be the wave function associated with a particle in motion. The
three-dimensional time-independent Schr𝑜̈ dinger equation is
ħ2
-2𝑚 ∇2 𝜓 + V𝜓 = E𝜓
ħ2
or, [− 2𝑚 ∇2 + V ] ψ = E𝜓 ------------ (8)
̂ 𝜓 = E𝜓
or, 𝐻
In Eqn. (8) we find:
i) On the left-side, the operator is Hamiltonian operator which operates on
the wave function 𝜓(𝑥, 𝑦, 𝑧).
ii) on the right-side, E𝜓 is the product of the total energy E and the wave
function 𝜓.
Thus the Hamiltonian operator operating on the wave function reproduces
the same function multiplied by the total energy E.
Therefore, the solutions of the time-independent Schrodinger equation are the-
functions of the Hamiltonian operator, and the eigen-values E of the operator are
the only possible values of the total energy that a quantum mechanical system may
possess.
The Postulates of Quantum Mechanics

Postulate I: Wavefunctions
 The state of a quantum mechanical system is completely specified by the
wave function Ψ(r, t).
 The wave function contains information about all the properties of the system
that are subject to experimental determination.
 The wave function depends on the spatial coordinates of all the particles that
constitute the system and on time: the time-independent wave function is ψ
whilst the time dependent one is Ψ.
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 The wave function is either a real or a complex number.
 The wave function itself has no physical meaning, but its square modulus,
|ψ|2 (when real) or ψ*ψ (when complex) represents the probability density or
distribution for the system as suggested by Max Born.
 The wave function must satisfy the condition that finding the particle
somewhere in space is and this gives us the normalization condition,
Postulate II: Quantum Mechanical Operators

With every observable dynamical quantity there is an operator. The operators
corresponding to the pertinent dynamical quantities are:
All the operators have eigen-functions and eigen-values.

The Method of Forming the Schrodinger Wave Equations
i) Time-dependent Schrodinger wave equation
We equate the two operators for the total energy E:
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ħ2
− 2𝑚 ∇2 + V = i ħ 𝜕𝑡𝜕
Now we multiply the both sides by 𝛙(x,y,z,t)
ħ2
− 2𝑚 ∇2 ψ + V 𝛙= i ħ 𝜕𝑡𝜕 𝛙
This is the required equation.
ii) Three Dimensional Time-Independent Schrodinger Wave Equation
We assume 𝜓(x,y,z) to be the eigen-function of the total energy operator
ħ2
− 2𝑚 ∇2 + V =E
Therefore, we get
ħ2
− 2𝑚 ∇2 ψ + V𝜓 =E𝜓
This is the requred equation.
Postulate III: Eigenfunction-eigenvalue relationship

In any measurement of the observable associated with operator Â the only values
that will ever be observed are the eigenvalues a that satisfy the eigen value
equation
Postulate IV: Average or Expectation value

The average value of many measurements of an observable A, when the system is
described by function ψ, is equal to the expectation value <A> , which is defined as
follows,
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If the wavefunction ψ is normalized, i.e., ∫ 𝜓 ∗ 𝜓 𝑑𝑉 = 1, then
Postulate V: Evolution of wavefunction with time

The time-dependent Schr¨odinger equation governs the time evolution of a
quantum mechanical system:
Orthogonality of Eigen-functions
Let 𝜓𝑚 (x) and 𝜓𝑛 (x) be any two normalised non-degenerate eigen functions of the
one-dimensional Schrodinger equation for a bound particle with corresponding
eigen values Em and En. The eigen functions always show the property of
orthogonality, i.e., they always obey the equation.
∞
∫−∞ 𝜓𝑚 * 𝜓𝑛 dx =0 if m ≠ 𝑛 -------------- (1)
and
∞
∫−∞ 𝜓𝑚 * 𝜓𝑛 dx =1 if m = 𝑛 if m=n -------- (2)
Example: The eigenfunctions of a particle in a one-dimensional box can be expressed as

2 𝜋
𝜓1 (𝑥) = √𝐿 sin ( 𝐿 ) 𝑥
and
2 2𝜋
𝜓2 (𝑥) = √𝐿 sin ( 𝐿 ) 𝑥.
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Show that they are orthogonal to one another.
Soln.
∞ ∞ 2 𝜋 2 2𝜋
∫−∞ 𝜓1 𝜓2 𝑑𝑥 = ∫−∞ (√𝐿 sin (𝐿 ) 𝑥 √𝐿 sin ( 𝐿 ) 𝑥) 𝑑𝑥
2 ∞ 1 𝜋 3𝜋
= 𝐿 ∫−∞ 2 [cos (𝐿 ) 𝑥 − cos ( 𝐿 ) 𝑥] 𝑑𝑥
𝜋 3𝜋 ∞
1 sin( 𝐿 )𝑥 sin(
𝐿
)𝑥
= [ 𝜋 − 3𝜋 ]
𝐿
𝐿 𝐿 −∞
= [𝜋(∞ + ∞) − 3𝜋(∞ + ∞)]

= 0.
Example: The state of a free particle is represented by a wave function

𝑥2
− +𝑖𝑘𝑥
𝛹(x,0) = N 𝑒 2𝑎2
a) Find out the factor N, b) In what region of space the particle is most likely
to be found?
Soln.
The factor is simply the normalization constant. The normalization condition is
∞
∫−∞|𝛹(𝑥, 0)|2 dx =1
L.H.S
2
∞ −𝑥
|𝑁| 2
∫−∞ 𝑒 𝑎2 dx = |𝑁|2 a√𝜋
∴ |𝑁|2 a√𝜋 =1
1
Where, N = 1 1
𝜋4 𝑎2
b) The probability density is given by

−𝑥2
|𝛹(𝑥, 0) = |𝑁| |2 2
𝑒 𝑎2
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This probability is maximum at x= 0 and for |𝑥|> a, it decreases exponentially.
Thus we can say that the particle is most likely to be found in a region in a width a
on either side of the origin, x= 0.
The Parity Operator

We can have a wave function with the following properties
Class I:
ψ(x)  ψ( x)
and
Class II:
ψ(x)  ψ(x) .
This is a consequence of an interesting property of the Hamiltonian.
Let us consider a general Hamiltonian
where
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V (x)  V (x) .
The Schrödinger equation is
Ĥψ  Eψ
and due to the symmetry of V (x) , we find that whenever ψ(x) is a solution then so is
Some Problems
1. A particle is in motion along a line between x= 0 and x= a with zero
potential energy, and at points for which x<0 and x>a the potential energy is
infinite. The wave function for the particle in the nth state is given by
n x
 n  A sin
a
Find the expression for the normalized wave function.

Solution:
For the nth state the probability that the particle will be between x and x+dx is
n x
Pn dx   n ( x) dx  A2 sin 2
2
dx
a
a
 Pn dx    n ( x) dx  1
2
Therefore,
0
n x
a
or, 
0
A2 sin 2
a
dx  1
20
1  2 nx 
a
or 
201  cos
a 
dx  1
a
A2  2 nx 
a
a
or,   x
2 0  2 n
sin
a  0
1
The second term of the integrated expression is zero at both the limits.
Therefore, (A2/2) a =1
2
so, A 
a
The normalized wave function is
2 n x
 n ( x)  sin
a a
2.
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3.
22
4.
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5. Find the eigenvalues and eigen-functions of the operator d/ dx.
10.
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2. Quantum Postulates

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Importance of the Hamiltonian Operator

The Postulates of Quantum Mechanics

Postulate II: Quantum Mechanical Operators

All the operators have eigen-functions and eigen-values.

Now we multiply the both sides by 𝛙(x,y,z,t)

ii) Three Dimensional Time-Independent Schrodinger Wave Equation

We assume 𝜓(x,y,z) to be the eigen-function of the total energy operator

Postulate III: Eigenfunction-eigenvalue relationship

Postulate IV: Average or Expectation value

Postulate V: Evolution of wavefunction with time

Example: The eigenfunctions of a particle in a one-dimensional box can be expressed as

= [𝜋(∞ + ∞) − 3𝜋(∞ + ∞)]

Example: The state of a free particle is represented by a wave function

b) The probability density is given by

The Parity Operator

The Schrödinger equation is

Find the expression for the normalized wave function.

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