Partition function of simple system

In summary, the conversation discusses finding the partition function and the limit of energy for a molecule with 4 states of energy as temperature approaches infinity. The calculation is shown and it is determined that the equipartition theorem does not apply in this scenario. An alternative method of expanding the exponential is suggested.
  • #1
unscientific
1,734
13

Homework Statement



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A molecule has 4 states of energy -1, 0,0 and 1. Find its partition function and limit of energy as T → ∞.

Homework Equations


The Attempt at a Solution



[tex]Z = \sum_r e^{-\beta E} = e^{-\beta} + 2 + e^{\beta}[/tex]

[tex]U = -\frac{\partial ln(Z)}{\partial \beta} = \frac{e^{-\beta} - e^{\beta}}{e^{-\beta} + 2 + e^{\beta}}[/tex]

As ##T→\infty##, ##exp(-\beta) \approx 1 - \beta## and ##exp(\beta) \approx 1 + \beta##.

Thus,
[tex]U \approx \frac{(1-\beta) - (1+\beta)}{2 + (1+\beta) + (1-\beta)} = -\frac{\beta}{2} = -\frac{1}{2kT}[/tex]

The equipartition theorem should take over with Energy = 4 * (1/2)kT = 2kT = 2/β.
But instead I'm getting -β/2.
 
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  • #2
bumpp
 
  • #3
Ammm, okay...

Your calculation is right, at least I got the same result for ##U##.

my comment about the equipartition theorem: My experiences are that you really have to master thermodynamics to completely understand this theorem. Lots of results can be "guessed" if you truly understand the concept. I was never that good at it therefore I always had to do the long calculations.
Ok, now to tell something that is actually useful:

from http://chemwiki.ucdavis.edu/Physical_Chemistry/Statistical_Mechanics/Equipartition_Theorem (Degrees of freedom):
"The law of equipartition of energy states that each quadratic term in the classical expression for the energy contributes ½kBT to the average energy."

Let's take a molecule of ideal gas for example: One molecule has in fact ##6## degrees of freedom. ##3## of them precisely describe it's position and are called coordinates (x,y,z), the other ##3## are of course components of momentum (note that momentum is quadratic in energy ##E_k=\frac{p^2}{2m}##). Each component of momentum therefore contributes ##\frac{1}{2}kT##, so the average energy of molecule of ideal gas is ##\frac{3}{2}kT##.

I guess all I am trying to say is that you have no quadratic degrees of freedom and therefore your calculation using equipartition theorem is wrong.

ps: Keep in mind that I never mastered that theorem. I hope I didn't just make a fool out of myself.
 
  • #4
try expanding the exponential in different form
 
  • #5
Exp(-x) = 1/ exp(x) = 1/ (1+x)

try in this form and show what you get, i hope this work
 

Related to Partition function of simple system

1. What is the partition function of a simple system?

The partition function of a simple system is a mathematical function that describes the distribution of energy among the different possible states of the system. It is a fundamental concept in statistical mechanics and is used to calculate various thermodynamic properties of the system, such as the average energy and entropy.

2. How is the partition function calculated?

The partition function is calculated by summing over all possible states of the system, with each state weighted by the Boltzmann factor, which is equal to e^(-E/kT), where E is the energy of the state, k is the Boltzmann constant, and T is the temperature of the system.

3. What is the significance of the partition function?

The partition function is significant because it allows us to calculate important thermodynamic properties of a system, such as the average energy and entropy. It also provides a link between the microscopic behavior of individual particles and the macroscopic behavior of the entire system.

4. Can the partition function be used for complex systems?

Yes, the partition function can be used for both simple and complex systems. However, for more complicated systems, the calculation of the partition function may become more difficult and may require advanced mathematical techniques or computer simulations.

5. How does the partition function relate to the free energy of a system?

The partition function is related to the free energy of a system through the following equation: F = -kTln(Z), where F is the free energy, k is the Boltzmann constant, T is the temperature, and Z is the partition function. This equation is known as the Helmholtz free energy formula and is used to calculate the free energy of a system at constant temperature.

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