Entropy and partition function

In summary, the conversation discusses the possibility of obtaining the relation S = \log Z + \langle U \rangle /T directly from the Boltzmann distribution. It is proposed that this can be achieved by using the VN entropy and the entropy of a single microstate. There is a small mathematical trick involved in this process. The conversation also delves into the connection between entropy in the microcanonical and canonical ensembles. It is suggested that this can be explicitly seen by writing the partition function using the steepest descent method. Finally, it is mentioned that the thermodynamic potential for a system in thermal contact with a bath is Helmotz's free energy F and the last term in the equation is the mean value of energy divided by
  • #1
Euclid
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0
Is it possible to obtain the relation
[tex] S = \log Z + \langle U \rangle /T[/tex]
directly from the Boltzmann distribution?

Edit: It seems that we can if we use the VN entropy:
[tex] S = -\Sigma p_i \log p_i [/tex]
This suggests that the entropy of a single microstate should be
[tex] s = -\log( \frac{e^{-\epsilon \beta}}{Z})[/tex]

Is there some way to justify this last formula?
 
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  • #2
Using log rules the last line becomes
ln(Z) +epsilom.beta
the justifying the fact that epsilom /(kT) implies <U>/T
Does this help , is epsilom the energy of the particular state?
 
  • #3
Yes epsilon is the energy of some particular state. My question is, is there some way to arrive at [tex] s = -\log (e^{-\epsilon \beta}/Z)[/tex] from the more familiar definition [tex] S = \log \Omega[/tex], where omega is the number of accessible microstates?
 
  • #4
I just gave it a fair whack.
Got S/k=Z+sum{beta.E.exp(-beta.E)/Z}
Have done stat. mech. for about a year so I am a bit rusty. Does this help?
My experience is that somewhere along the way lies a small math trick that helps, just getting to know it is hard
 
  • #5
NoobixCube said:
I just gave it a fair whack.
Got S/k=Z+sum{beta.E.exp(-beta.E)/Z}
Have done stat. mech. for about a year so I am a bit rusty. Does this help?
My experience is that somewhere along the way lies a small math trick that helps, just getting to know it is hard

Yes I have already been that far. I think you mean [tex]\log Z[/tex] in the first term.

In any event, I think I have figured this one out. In the microcanonical ensemble, the entropy of a state is given by [tex] \log N[/tex] where N is the number of accessible microstates. This can be rewritten as [tex] \log N = - \Sigma \log \left(\frac{1}{N}\right) = - \Sigma_i \log p_i[/tex]. The last line follows from the fundamental assumption that a system is equally likely to be in any of its accessible microstates. Thus, in the canonical ensemble, the appropriation generalization is the formula given above.

All I was trying to do here was to see explicitly the connection between entropy in these two ensembles.
 
  • #6
You can just write the partition function as

[tex]Z = \int dE \Omega\left(E\right)\exp\left(-\beta E\right)[/tex]

Next, take the log of the integrand and expand around the maximum, so you write it as exp(expansion of log) (i.e. you use the the steepest descent method). You obtain the relation as the leading order term that becomes exact in the thermodynamic limit.
 
  • #7
The thermodynamic potential for a system in thermal contact with a bath is Helmotz's free energy F:

dF=-SdT-pdV

so [tex]S=-\frac{\partial F}{\partial T}[/tex]

but [tex]F=\frac{-1}{\beta}lnZ[/tex]

[tex]S=klnZ+\frac{1}{\beta Z}\frac{\partial Z}{\partial T}[/tex]

and the last term is the mean value of energy / T.
 

What is entropy?

Entropy is a measure of the disorder or randomness of a system. It is a thermodynamic property that describes the amount of energy in a system that is unavailable for doing work.

How is entropy related to the partition function?

The partition function is a mathematical tool used to calculate the thermodynamic properties of a system, including entropy. The partition function takes into account the different possible energy states of a system and their probabilities, which are used to calculate the system's entropy.

What is the significance of the partition function in statistical mechanics?

The partition function is essential in statistical mechanics as it allows for the calculation of various thermodynamic properties, including entropy, of a system. It provides a link between the microscopic behavior of particles and the macroscopic properties of a system.

What factors affect the value of the partition function?

The value of the partition function is affected by the number of particles in a system, the different energy states available to those particles, and the temperature of the system. It also depends on any external forces or constraints acting on the system.

How does the partition function change with temperature?

The partition function is directly proportional to temperature. As the temperature of a system increases, the number of available energy states also increases, resulting in a larger partition function. This, in turn, leads to an increase in the system's entropy.

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