Partition function of simple system

AI Thread Summary
The discussion centers on calculating the partition function for a molecule with four energy states: -1, 0, 0, and 1. The partition function is derived as Z = e^(-β) + 2 + e^(β), leading to the internal energy U = - (e^(-β) - e^(β)) / (e^(-β) + 2 + e^(β)). As temperature approaches infinity, the calculations suggest that U approximates to -β/2, which contrasts with the expected result from the equipartition theorem of 2kT. Participants emphasize the importance of mastering thermodynamics to fully understand the equipartition theorem, noting that the absence of quadratic degrees of freedom affects the application of the theorem in this case. The conversation concludes with suggestions for alternative approaches to the exponential calculations.
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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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bumpp
 
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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