Partition function of simple system

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Homework Help Overview

The problem involves calculating the partition function for a molecule with four energy states: -1, 0, 0, and 1. The original poster attempts to find the partition function and analyze the limit of energy as temperature approaches infinity.

Discussion Character

  • Exploratory, Conceptual clarification, Mathematical reasoning

Approaches and Questions Raised

  • Participants discuss the calculation of the partition function and the average energy U. Some express agreement with the original poster's calculations while questioning the application of the equipartition theorem in this context. Others suggest alternative approaches, such as expanding the exponential function.

Discussion Status

The discussion is ongoing, with participants sharing their calculations and insights. Some guidance has been offered regarding the equipartition theorem and its applicability, but no consensus has been reached on the correct interpretation of the results.

Contextual Notes

Participants note the complexity of mastering thermodynamics and the equipartition theorem, indicating that assumptions about degrees of freedom may be under scrutiny. There is also mention of the need for clarity regarding the nature of the energy states involved.

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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



Z = \sum_r e^{-\beta E} = e^{-\beta} + 2 + e^{\beta}

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

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

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

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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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.
 
try expanding the exponential in different form
 
Exp(-x) = 1/ exp(x) = 1/ (1+x)

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

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