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Application of Quantum in Chemistry

The document discusses applying quantum mechanics concepts to model particles in boxes. It explains that [1] particles in boxes have quantized, discrete energy levels rather than a continuous spectrum, [2] the lowest energy level is not zero due to the uncertainty principle, and [3] the particle's wavefunction and probability density are structured with regions of higher and lower probability rather than being uniformly distributed. Examples are provided to calculate energy levels and determine the most probable locations of a particle in different quantum states.

Uploaded by

Rahul Singh
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© © All Rights Reserved
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
240 views

Application of Quantum in Chemistry

The document discusses applying quantum mechanics concepts to model particles in boxes. It explains that [1] particles in boxes have quantized, discrete energy levels rather than a continuous spectrum, [2] the lowest energy level is not zero due to the uncertainty principle, and [3] the particle's wavefunction and probability density are structured with regions of higher and lower probability rather than being uniformly distributed. Examples are provided to calculate energy levels and determine the most probable locations of a particle in different quantum states.

Uploaded by

Rahul Singh
Copyright
© © All Rights Reserved
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Application of quantum in chemistry

The Particle in A Box


The ‘Classical’ Case
The ‘Quantum’ Case
The absolutely small particle in the nanometer size box is a quantum particle,
and it must obey the Uncertainty Principle, that is, ΔxΔp= h/4π. If V=0 and x=
L/2, we know both x and p. The result would be ΔxΔp 0, the same as the classical
racquetball.

This is impossible for a quantum system. Therefore, V cannot be zero. The


particle cannot be standing still at a specific point. If V cannot be zero, then Ek
can never be zero. The Uncertainty Principle tells us that the lowest energy that a
quantum racquetball can have cannot be zero. Our quantum racquetball can
never stand still.
Energies of a Quantum Particle in a Box
Wave functions must be zero at the walls
Nodes are the points where the wave function crosses zero
Energies are quantized
A Discreet set of energy levels
Why are Cherries Red and Blueberries blue ?
The Colour of Fruit

This energy corresponds to

Deep Red Colour

If L=0.7 nm, =540 nm Green Colour


If L=0.6 nm, =397 nm Blue Colour
Particle in a box

Step 1: Define the potential energy

Step 2: Solve the Schrodinger equation

Step 3: Define the wave function

Step 4: Determine the allowed energies

Step 5: Interpret its meaning


Particle in 1-dimensional box

• Infinite walls Time Independent Schrödinger Equation

  2 d 2 ( x)
2
 V ( x)  E
2m dx
Region I Region II Region III KE PE TE

Applying boundary conditions:


V(x)=∞ V(x)=0 V(x)=∞

Region I and III:

L   2 d 2 ( x)
0 x
2
  *  E
2m dx
  0
2
d 2 ( x ) 2mE
2
 2
 ( x) Second derivative of a function equals a
dx negative constant times the same function.

Functions with this property sin and cos.


d 2 sin(ax )
2
 a 2 sin(ax )
dx

d 2 cos(ax )
 a 2 cos(ax )
dx

Copyright – Michael D. Fayer, 2007


b) x=L ψ=0
Region II: 0  Asin kL
  2 d 2 ( x) ButA  0
2
 E
2m dx
kL  n
d 2 ( x) 2m
  2
 2
E Thus, wave function:
dx 
This is similar to the general differential equation: nx
 II  A sin
L
d 2 ( x)
 2
 k 2
dx But what is ‘A’?
  A sin kx  B cos kx
Applying boundary conditions:

a) x=0 ψ=0
0  A sin 0k  B cos 0k
0  0  B *1
 B  0
Normalizing wave function: Calculating Energy Levels:
L


2mE
( A sin kx) 2
dx  1 k2 
0
2
L
 x sin 2kx  k 2 2
A    1
2

 2 4 k 0 E
2m
 n 
sin 2 L
2L L
A    1 k 2h2 h
2 n E (  )
 4  2m4 2 2
 L 

2 L 
A   1 n 2 2 h2
2 E
L2 2m4 2
2
A 
L
Thus normalized wave function is: Thus Energy is:

2 nx n2h2
 II  sin E
L L 8mL2
Particle in a 1-Dimensional Box

nx nx 
2
2 2
 II   II   sin
2
sin 
L L L L 

1) Difference b/w adjacent


energy levels:

2) Non-zero zero point energy

+ + 3) Probability density is structured


+ with regions of space demon-
-strating enhanced probability.
-
At very high n values, spectrum
becomes continous-
+ +
convergence with CM
(Bohr’s correspondance
principle)
E  *
Particle in a 3-D box
Question: An electron is in 1D box of 1nm length. What is the probability of
locating the electron between x=0 and x=0.2nm in its lowest energy state?
Question: An electron is in 1D box of 1nm length. What is the probability of
locating the electron between x=0 and x=0.2nm in its lowest energy state?

Solution:
Question: What are the most likely
locations of a particle in a box of length L
in the state n=3
Example: What are the most likely locations of a particle in a box of length L in
the state n=3
Expectation value of position and its
uncertainty
Expectation values

Position

Uncertainity
Expectation value of Momentum

And square of momentum


Momentum
Estimating pigment length

Assumptions:
Wavelength of transition for Anthracene

Particle in a Box Simple model of molecular energy levels.


Anthracene  electrons – consider “free”
in box of length L.
Ignore all coulomb interactions.

L 
L6 A
Pigments and Quantum mechanics

High degree of conjugation!!

• Electrons have wave properties and they don’t jump off the pigments when they reach its ends.

• These electrons resonances determine which frequencies of light and thus which colors, are absorbed
& emitted from pigments
Electron resonances in a cyclic conjugated molecule

A crude quantum model for such molecules assumes that electrons move freely in a ring.

Resonance condition:

R: radius of molecule, λ wavelength of electron


Energy is once again quantized. It depends on variable n which posseses
discrete values only

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