Finding the partition function

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The discussion revolves around calculating the internal energy, Helmholtz free energy, and entropy for a solid of N localized, non-interacting molecules with three quantum states. The initial attempt at finding the internal energy (U) involved averaging the energies of the states, but there was confusion regarding the correct application of the partition function (Z). The correct expression for Z was identified as Z = 1 + 2e^(-ε/kT), leading to a refined calculation of U. The participants clarified that the correct method involves using probabilities derived from Z to compute U accurately. The final expression for U was adjusted to U = (2Nεe^(-εβ))/(1 + 2e^(-εβ)).
S_Flaherty
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Homework Statement


Consider a solid of N localized, non-interacting molecules, each of which has three quantum states with energies 0, ε, ε, where ε > 0 is a function of volume.


Question: Find the internal energy, Helmholtz free energy, and entropy.


Homework Equations


Z = Ʃe-E(s)/kT
U = -N(dlnZ/dβ)
S = U/T + NklnZ
F = U - TS = -NkTlnZ


The Attempt at a Solution


For the internal energy would I just multiply N by the average energy?
So U = N((0 + ε + ε)/3) = 2Nε/3?

I also know there are equations for the three of these values that require the partition function, Z.

I know Z = Ʃe-E(s)/kT so would this just be
Z = 1 + e-ε/kT + e-ε/kT = 1 + 2e-ε/kT
U = -N(dlnZ/dβ)
lnZ = ln(1) + ln(2e-ε/kT) = ln2 - εβ, so U = Nε...

Which one of those solutions for U is the correct one? Or am I wrong in both cases?
 
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Second is right technique, although you've mathed wrongly.

for three states: 0, 1, 2
U = avg energy = E(0) P(0) + E(1) P(1) + E(2) P(2)

For E(0)=0, E(1)=E(2) =ε,
and P(energy) = exp(-energy/kT)/Z
P(0) = 1/Z, P(1)=P(2)=exp(-ε/kT)/Z
 
qbert said:
Second is right technique, although you've mathed wrongly.

for three states: 0, 1, 2
U = avg energy = E(0) P(0) + E(1) P(1) + E(2) P(2)

For E(0)=0, E(1)=E(2) =ε,
and P(energy) = exp(-energy/kT)/Z
P(0) = 1/Z, P(1)=P(2)=exp(-ε/kT)/Z

So, I get U = 2εe-ε/kT/Z

I just figured out something I did wrong with Z. dlnZ/dβ = (-2εe-εβ)/(1 + 2εe-εβ) so U = (2Nεe-εβ)/(1 + 2εe-εβ) ? Or did I mess something up?
 
Last edited:

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