Heat capacity of perturbed harmonic oscillator
Posted by peeterjoot on March 11, 2013
This problem was suggested as prep for the second midterm, but I spent too much time on my problem set. That’s pretty unfortunate since this showed exactly the approach that was expected for the second midterm problem. Not hard, just not obvious in the heat of the moment how to do that Taylor expansion.
Question: Anharmonic oscillator ( pr 3.29)
The potential energy of a one-dimensional, anharmonic oscillator may be written as
where , , and are positive constant; quite generally, and may be assumed to be very small in value.
Show that the leading contribution of anharmonic terms to the heat cpacity of the oscillator, assumed classical, is given by
To the same order, show that the mean value of the position coordinate is given by
Our partition function is
How to expand this wasn’t immediately clear to me (as it wasn’t on the midterm either). We can’t Taylor expand in , because there’s no single position that is of interest to expand around (we are integrating over all ). What we can do though is Taylor expand about the values and , which are assumed to be small. Here’s the two variable Taylor expansion of this perturbed harmonic oscillator exponential. With
The expansion to second order is
This can now be integrated by parts, where any odd powers are killed. For even powers we have
This gives us
Retaining only the first two terms of the expansion, we have
Our average energy, in this approximation
So to first order in our specific heat is
For the coordinate
Compare this to the expectation of the coordinate for an unperturbed harmonic oscillator
We now have a temperature dependence to the expecation of the coordinate that we didn’t have for the harmonic oscillator.
 RK Pathria. Statistical mechanics. Butterworth Heinemann, Oxford, UK, 1996.