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Postulate

This document discusses quantum mechanical concepts like probability, wave functions, eigenvalues, and eigenfunctions. It provides examples of applying operators to find eigenvalues of different eigenfunctions. It also discusses how to check if a wave function is acceptable by evaluating it at the boundaries of the given region. Finally, it shows how to calculate the average value of a quantity by taking the integral over the given region.

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16 views

Postulate

This document discusses quantum mechanical concepts like probability, wave functions, eigenvalues, and eigenfunctions. It provides examples of applying operators to find eigenvalues of different eigenfunctions. It also discusses how to check if a wave function is acceptable by evaluating it at the boundaries of the given region. Finally, it shows how to calculate the average value of a quantity by taking the integral over the given region.

Uploaded by

i 3l3j
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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CHEM 311

Chapter: 15

(Postulate)
Probability (P) is given by:

𝑷 = ∫ 𝝍𝟐 𝒅𝒙

For a particle confined in a box:


𝒂 𝒐𝒓 𝑳
𝑷=∫ 𝝍𝟐 𝒅𝒙
𝟎

𝒂 𝒐𝒓 𝑳
𝑷 = ∫𝟎 𝝍𝟐 𝒅𝒙 = 𝟏 (Normalized form)
What is 𝜳?

𝟐 𝒏𝝅𝒙
𝚿𝒏 𝒙 = 𝐬𝐢𝐧 ,
𝑳 𝑳
𝒇𝒐𝒓 𝒏 = 𝟏, 𝟐, 𝟑, …
Question-1
Given that the wave function is described as:

𝟐 𝒏𝝅𝒙
𝜳𝒏 (𝒙) = √ 𝒔𝒊𝒏 ( )
𝑳 𝑳

For the ground state level, calculate the probability of finding an


electron in the region between 0 and L/2.
(Hint: the standard integral of

Solution:

𝑷 = ∫ 𝝍𝟐 𝒅𝒙

𝑳/𝟐
𝟐 𝟐
𝒏𝝅𝒙
𝑷=∫ 𝒔𝒊𝒏 ( ) 𝒅𝒙
𝟎 𝑳 𝑳

For Ground state, n = 1:


𝑳/𝟐
𝟐 𝝅𝒙
𝑷=∫ 𝒔𝒊𝒏𝟐 ( ) 𝒅𝒙
𝟎 𝑳 𝑳

𝝅
By using the hint, 𝒂 = 𝑳 :

𝑳/𝟐
𝟐 𝒙 𝟏 𝟐𝝅𝒙
𝑷= [ − × 𝒔𝒊𝒏 ( )]
𝑳 𝟐 𝟒×𝝅 𝑳
𝑳 𝟎
𝑳/𝟐
𝟐 𝒙 𝑳 𝟐𝝅𝒙
𝑷= [ − × 𝒔𝒊𝒏 ( )]
𝑳 𝟐 𝟒×𝝅 𝑳 𝟎

Substitute:
𝑳/𝟐
𝒙 𝟏 𝟐𝝅𝒙
𝑷=[ − × 𝒔𝒊𝒏 ( )]
𝑳 𝟐×𝝅 𝑳 𝟎

Solve:

𝟏 𝟏 𝟏
𝑷= − × 𝒔𝒊𝒏(𝝅) − 𝟎 = = 𝟎. 𝟓 = 𝟓𝟎%
𝟐 𝟐×𝝅 𝟐
Question-2
Given that the wave function is described as:
𝝅𝒙
𝝍(𝒙) = 𝑪 𝒔𝒊𝒏 ( )
𝒂
What is the value of C?
(Hint: the standard integral of

Solution:
𝒂
𝑷 = ∫ 𝝍𝟐 𝒅𝒙 = 𝟏
𝟎
Substitute:
𝒂
𝝅𝒙
𝑷 = ∫ 𝑪𝟐 𝒔𝒊𝒏𝟐 ( ) 𝒅𝒙 = 𝟏
𝟎 𝒂

𝒂
𝟐
𝝅𝒙
𝑪 ∫ 𝒔𝒊𝒏𝟐 ( ) 𝒅𝒙 = 𝟏
𝟎 𝒂

𝒂
𝝅𝒙 𝟏
∫ 𝒔𝒊𝒏𝟐 ( ) 𝒅𝒙 =
𝟎 𝒂 𝑪𝟐
By using the hint:
𝒂
𝒙 𝟏 𝟐𝝅𝒙 𝟏
[ − 𝒔𝒊𝒏 ( )] =
𝟐 𝟒×𝝅 𝒂 𝑪𝟐
𝒂 𝟎

Evaluate:

𝒂 𝟏
[ − 𝒔𝒊𝒏(𝟐𝝅) − 𝟎] = 𝟐
𝟐 𝑪
𝒂 𝟏 𝟐
= 𝟐 ⇒ 𝑪𝟐 =
𝟐 𝑪 𝒂

𝟐
𝑪=√
𝒂
Question-3
Given that the wave function is described as:
𝝅𝒙
𝝍(𝒙) = 𝑪 𝒔𝒊𝒏 ( )
𝒂
What is the normalized form of the function?
(Hint: the standard integral of
Solution:

𝟐 𝝅𝒙
√ 𝒔𝒊𝒏 ( )
𝒂 𝒂
Is the function an acceptable wave function confined in a
box or not?

Simply!!
Evaluate the function at 𝒙 = 𝟎 and 𝒙 = 𝒂.

If both cases result in (0), then it is acceptable. Otherwise, it


is not.

Try this:

𝝍(𝟎) = 𝟎 + 𝟎 = 𝟎
𝝍(𝒂) = 𝒄 𝒔𝒊𝒏(𝝅) + 𝒅 𝒔𝒊𝒏(𝟐𝝅) = 𝟎
It is an acceptable wave function.

Now try this:


𝝍 = 𝐜𝐨𝐬(𝟑𝝅𝒙/𝒂 )
𝝍(𝟎) = 𝟏 ≠ 𝟎
c cannot equal zero. Therefore, it is an unacceptable wave
function.
What is eigenvalue and eigenfunction?

Suppose that I have an operator for ALI (A) and it is given


by:
𝒅𝟐
𝟑 𝟐
𝒅𝒙

Also suppose that my function is:


𝝍 = 𝒔𝒊𝒏(𝒙)

Apply the operator to the function:


𝒅𝟐 𝒅𝟐
𝟑 𝟐 (𝝍) = 𝟑 𝟐 (𝒔𝒊𝒏(𝒙))
𝒅𝒙 𝒅𝒙

Derive:
𝒅𝟐 𝒅
𝟑 𝟐 (𝒔𝒊𝒏(𝒙)) = 𝟑 (𝒄𝒐𝒔(𝒙))
𝒅𝒙 𝒅𝒙
Again:
−𝟑𝒔𝒊𝒏(𝒙)
Notice!!!
−𝟑𝒔𝒊𝒏(𝒙) = −𝟑𝝍
Therefore, −𝟑 is the eigenvalue of the eigenfunction (𝝍)

Let’s try another function, let’s say:


𝝍 = 𝟒𝒔𝒊𝒏(𝟐𝒙)

Apply the operator to the function:


𝒅𝟐 𝒅𝟐
𝟑 𝟐 (𝝍) = 𝟑 𝟐 (𝟒𝒔𝒊𝒏(𝟐𝒙))
𝒅𝒙 𝒅𝒙

Derive:
𝒅𝟐 𝒅 𝒅
𝟑 𝟐 (𝟒𝒔𝒊𝒏(𝟐𝒙)) = 𝟑 (𝟖𝒄𝒐𝒔(𝟐𝒙)) = 𝟐𝟒 (𝒄𝒐𝒔(𝟐𝒙))
𝒅𝒙 𝒅𝒙 𝒅𝒙

Again:
−𝟒𝟖𝒔𝒊𝒏(𝟐𝒙)

Multiply by 4 and divide be 4:


𝟒𝟖
−𝟒𝟖𝒔𝒊𝒏(𝟐𝒙) = − × (𝟒𝒔𝒊𝒏(𝟐𝒙)) = −𝟏𝟐 × (𝟒𝒔𝒊𝒏(𝟐𝒙))
𝟒
Notice!!!
−𝟏𝟐 × (𝟒𝒔𝒊𝒏(𝟐𝒙)) = −𝟏𝟐𝝍
Therefore, −𝟏𝟐 is the eigenvalue of the eigenfunction (𝝍)
Solution:

Apply the operator of kinetic energy on the function:


ℏ𝟐 𝒅𝟐 𝟏
− ( 𝒔𝒊𝒏𝟐𝒙)
𝟐𝒎 𝒅𝒙𝟐 𝟐
ℏ𝟐 𝒅𝟐
=− 𝟐
(𝒔𝒊𝒏𝟐𝒙)
𝟒𝒎 𝒅𝒙

Derive:
ℏ𝟐 𝒅
− (𝟐𝒄𝒐𝒔𝟐𝒙)
𝟒𝒎 𝒅𝒙
ℏ𝟐 𝒅
=− (𝒄𝒐𝒔𝟐𝒙)
𝟐𝒎 𝒅𝒙
Derive again:
ℏ𝟐 𝒅 ℏ𝟐
=− (𝒄𝒐𝒔𝟐𝒙) = (𝒔𝒊𝒏𝟐𝒙)
𝟐𝒎 𝒅𝒙 𝒎

Multiply by 2 and divide be 2:


ℏ𝟐 𝟐ℏ𝟐 𝟏 𝟐ℏ𝟐
(𝒔𝒊𝒏𝟐𝒙) = ( 𝒔𝒊𝒏𝟐𝒙) = (𝝍)
𝒎 𝒎 𝟐 𝒎

𝟐
𝟏 𝟐ℏ
𝑲𝑬 = 𝒎𝒆 𝐕 𝟐 =
𝟐 𝒎𝒆
𝒉
∗ 𝑵𝒐𝒕𝒆: ℏ =
𝟐𝝅

You will get 𝐕 = 𝟐. 𝟑𝟏𝟓 × 𝟏𝟎−𝟒 m/s.


Usually, you will be asked to evaluate the average value for the region from 0
to a.
Postulate

Is it an
What is the Average value of
acceptable wave Eigenvalue
probability? ....
function?

Evaluate the
Find the constant function at 𝒙 =
or the 𝟎 and 𝒙 = 𝒂
normalized form.

𝑷 = ∫ 𝝍𝟐 𝒅𝒙

𝒂 𝒐𝒓 𝑳
𝑷=∫ 𝝍𝟐 𝒅𝒙 = 𝟏
𝟎

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