Question about Quantum + Thermodynamic Perturbation theory

In summary: Landau simply takes the derivative of the unperturbed Gibbs distribution with respect to the perturbation parameter:
  • #1
mSSM
33
1
The following comes from Landau's Statistical Physics, chapter 32.

Using a Hamiltonian
[tex]\hat{H} = \hat{H}_0 + \hat{V}[/tex]
we get the following expression for the energy levels of a perturbed system, up to second order:
[tex]E_n = E_0^{(0)} + V_{nn} + \sideset{}{'}{\sum}_m \frac{\lvert V_{nm}\rvert^2}{E_n^{(0)} - E_m^{(0)}}[/tex].
The prime signifies that the sum is done over all [itex]m\neq n[/itex].

Substituting this into the equation (from the normalisation of the Gibbs canonical distribution):
[tex]e^{-F/T} = \sum_0 e^{-E_n/T}[/tex].

This expression is then logarithmized and expanded in powers of [itex]V/T[/itex], so that we get:
[tex] F = F_0 + \sum_n V_{nn} w_n + \sum_n \sideset{}{'}{\sum}_m \frac{\lvert V_{nm}\rvert^2 w_n}{E_n^{(0)} - E_m^{(0)}} - \frac{1}{2T} \sum_n V^2_{nn} w_n + \frac{1}{2T} \left( \sum_n V_{nn} w_n \right)^2 [/tex],
where [itex]w_n = \exp\left\{(F_0 - E_n^{(0)}/T\right\}[/itex] is the unperturbed Gibbs distribution.

We can now notice that
[tex] \sum_n V_{nn} w_n \equiv \overline{V}_{nn} [/tex],
i.e., the sum is the mean of [itex]V[/itex] avaraged over the quantum state and the statistical distribution.

And now this is where it gets interesting, and where I fail to see something. Landau writes, that you can rewrite the equation for the free energy above in the following way:
[tex] F = F_0 + \overline{V}_{nn} - \frac{1}{2} \sum_n \sideset{}{'}{\sum}_m \frac{\lvert V_{nm}\rvert^2 (w_m - w_n)}{E_n^{(0)} - E_m^{(0)}} - \frac{1}{2T} \left\langle (V_{nn} - \overline{V}_{nn})^2 \right\rangle[/tex]

That makes perfect sense except for the part with the double-sum, where I don't understand how he obtains it:
[tex]\sum_n \sideset{}{'}{\sum}_m \frac{\lvert V_{nm}\rvert^2 w_n}{E_n^{(0)} - E_m^{(0)}}= -\frac{1}{2} \sum_n \sideset{}{'}{\sum}_m \frac{\lvert V_{nm}\rvert^2 (w_m - w_n)}{E_n^{(0)} - E_m^{(0)}}[/tex]

Is that even correct, or did I miss something? Can you tell me how he gets there? I have also looked up his derivation of the Quantum Perturbation theory, but it does not help me with this particular problem, unfortunately.
 
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  • #2
Split up the original double sum containing only w_n into two and rename the summation indices n<->m in the second one.
 
  • #3
Oh dear, thank you so much! I was going crazy over this... :D This is such a silly trick.
 

Related to Question about Quantum + Thermodynamic Perturbation theory

What is quantum perturbation theory?

Quantum perturbation theory is a mathematical framework used to study the effects of small perturbations on quantum systems. It allows us to approximate the behavior of a system that is not solvable exactly, by treating the perturbation as a small disturbance to a known system.

What is thermodynamic perturbation theory?

Thermodynamic perturbation theory is a mathematical framework used to study the effects of small perturbations on thermodynamic systems. It allows us to approximate the behavior of a system that is not solvable exactly, by treating the perturbation as a small disturbance to a known system.

How are quantum and thermodynamic perturbation theories related?

Quantum and thermodynamic perturbation theories are related in that they both use similar mathematical techniques to study the effects of small perturbations on systems. However, they are applied to different types of systems - quantum perturbation theory is used for quantum systems, while thermodynamic perturbation theory is used for thermodynamic systems.

What are the limitations of quantum and thermodynamic perturbation theories?

One limitation of both quantum and thermodynamic perturbation theories is that they are only accurate for small perturbations. If the perturbation is too large, the approximations made in the calculations may no longer hold. Additionally, these theories may not be applicable to highly non-linear systems or systems with strong interactions.

What are some real-world applications of quantum and thermodynamic perturbation theories?

Quantum perturbation theory has been used in many areas of physics, including quantum mechanics, quantum field theory, and quantum chemistry. Thermodynamic perturbation theory has applications in fields such as chemical engineering, materials science, and statistical mechanics. Both theories have also been applied to studying the properties of complex systems, such as proteins and polymers.

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