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09 Particle in 1-D Box PDF

1. The document discusses the particle in a 1-dimensional box model applied to π electrons in conjugated molecules. 2. In this model, π electrons are confined to a box of length defined by the carbon-carbon bond distances, with allowed energy levels calculated from the Schrodinger equation. 3. The model is used to calculate excitation energies for π → π* transitions in conjugated molecules, which approximate but do not exactly match experimental values due to assumptions made in the simple model.

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Sigit Priatmoko
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198 views

09 Particle in 1-D Box PDF

1. The document discusses the particle in a 1-dimensional box model applied to π electrons in conjugated molecules. 2. In this model, π electrons are confined to a box of length defined by the carbon-carbon bond distances, with allowed energy levels calculated from the Schrodinger equation. 3. The model is used to calculate excitation energies for π → π* transitions in conjugated molecules, which approximate but do not exactly match experimental values due to assumptions made in the simple model.

Uploaded by

Sigit Priatmoko
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Application of Quantum Theory

1- Particle in 1-D box.

The particle is free to move inside the box

Consider the ethylene molecule as an example of the free particle move


in 1-D box, in which the two electrons, only, are free to move, while the
electrons are frozen in bonds with atoms. The length of the box is twice
the C=C bond length.
V=0

V=0
H H

H
H

x=0 x=L
L = 2*1.4 =2.8 A
1- Schrodinger Equation is

( )

2- Using V=0

3- The solution of the 2nd order ordinary differential equation is


( ) ( )
4- For particle in box =0 at x =0 and =0 at x =L (boundary condition)
( ) ( )

( )
5- The last equation are mitts only if the argument of sin function is an
integer multiplier of (0, 180, 360 )

( )

6- Note that

7- The energies, wave functions and the probability densities are

Energy Level
Diagram
15

E 2

10

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
8- Comments
a. The energy increase as the quantum number increase
b. The energy separation between energy levels increase as the
quantum number increase
c. The energy and the energy separation increases as the size of the
box decreases
d. 2 < when have small values while 2 = when has the
maximum value. (why)
e. Node = the point where wave function passes through zero, or the
position where probability of finding particle = 0 (No. of nodes =
n-1)
f. The probability of finding the particle between two points x 1 and
x2 are different when n have small values, while as n increases (n
>100) these 2 probabilities become the same. Generally the
probability density become uniform as n increase, that is to say
quantum mechanics results and classical mechanics results tend to
agree in the limit of the large quantum numbers

9- The particle in a box model can be applied to electrons moving freely


( electrons) in a molecule
a. For example butadiene has an absorption band at 217 nm for the
1st * transition. As a simple approximation, consider
butadiene as being a 1-D box of length 4*1.4 = 5.6 . and
consider the 4 electrons to occupy the levels calculated using
the particle in box model H2C C C CH2 LUMO
H H
b. The calculated excitation energy is
E3

HOMO

E2
HOMO : Highest Occupied Molecular Orbital
LUMO : Lowest Unoccupied Molecular Orbital
E1
E=ELUMO EHOMO

( )

h (Plank Constant)= 6.626 x 10-34 JS, m (mass of electron)=9 x 10-31 Kg,


L (length of bonds = no. of carbons *1.4 , 1 =1 x10-10 m
c (speed of light)=3 x 108 m/S , 1 m = 109 nm
What are the causes of difference between Experimental value (217 nm) and
calculated value (204 nm)
That is due to the approximations done
1. Box length C=C equal C-C =1.4
2. Assume it linear

Calculate (nm) for the 1st * transition for the following compounds

Compound Ethylene Butadiene Hexatriene Octatetraene -carotene


No. of C's 2 4 6 8 22
Exp. 162 217 274 304 425
Calculated

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