Taylor expansion of an integral (for Thermodynamic Perturbations)

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SUMMARY

The discussion focuses on the Taylor expansion of an integral in the context of thermodynamic perturbation theory, specifically within the Gibbs distribution framework as outlined in chapter 32 of Landau's Statistical Physics. The integral expression for free energy, e^{-F/T} = \int e^{-(E+V)/T} \mathrm{d}\Gamma, is expanded to second order in perturbation V, leading to F = -T \log \bigl( \int e^{E/T} (1 - V/T + (V/T)^2) \mathrm{d}\Gamma \bigr). The main challenge discussed is how to properly apply Taylor expansion rules to integrals, particularly regarding the placement of variables within the integral.

PREREQUISITES
  • Understanding of thermodynamic perturbation theory
  • Familiarity with the Gibbs distribution and free energy concepts
  • Knowledge of Taylor series expansion
  • Basic proficiency in integral calculus
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  • Study the Taylor expansion of integrals in mathematical physics
  • Learn about perturbation theory applications in statistical mechanics
  • Explore advanced topics in Landau's Statistical Physics, particularly chapter 32
  • Investigate the relationship between integrals and sums in the context of perturbation expansions
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In thermodynamic perturbation theory (chapter 32 in Landau's Statistical Physics) for the Gibbs (= canonical) distribution, we have [itex]E = E_0 + V[/itex], where [itex]V[/itex] is the perturbation of our energy.

When we want to calculate the free energy, we have:
[tex]e^{-F/T} = \int e^{-(E+V)/T} \mathrm{d}\Gamma[/tex]

We can expand the expression inside the integral for small values of [itex]V[/itex] to second order we obtain:
[tex]e^{-F/T} = \int e^{E/T} (1 - V/T + (V/T)^2) \mathrm{d}\Gamma[/tex]

Now, the next step is to logarithmize this expression and then expand it in terms of [itex]V[/itex] again, to second order:
[tex]F = -T \log \bigl( \int e^{E/T} (1 - V/T + (V/T)^2) \mathrm{d}\Gamma \bigr)[/tex]

But now I am stuck. I don't understand how to expand this in a series. The zeroth order still works great, and I obtain [itex]-T \log \int e^{E/T} = F[/itex], which is just what I want. But from the first order onwards I am stuck:
What is the rule for Taylor expanding an integral? Especially, e.g., if I have [itex]f'(a) (x-a)[/itex] for first order, where exactly do I 'put' the [itex]x[/itex]? Inside the integral?
 
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So, I thought about this a little with a friend. I believe that I could see the integral as a sum, with a lot of different [itex]V_i[/itex], albeit them lying infinitesimally close to each other. Therefore, one could view the expansion with respect to [itex]V[/itex] as expansions with respect to a lot of different [itex]V_i[/itex] in this 'sum'. After this expansion one could imagine making the sum into an integral once more, such that the orders of [itex]V[/itex] are inside the integrals.
 

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