In the low-temperature limit (kT<<), each term in the rotational partition function is much smaller than the one before. Since the first term is independent of T, cut off the sum after the second term and compute the average energy and the heat capacity in this approximation. Keep only the largest T-dependent term at each stage of the calculation. Is your result consistent with the third law of thermodynamics? Sketch the behavior of the heat capacity at all temperature, interpolating between the high-temperature and low- temperature expressions.

Short Answer

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The graph is as follows,

Step by step solution

01

Step 1. Given Information

We are given that in the low-temperature limit (kT<<), each term in the rotational partition function is much smaller than the one before.

02

Step 2. Expanding the partition function 

Expanding the partition function by neglecting all higher order terms in the low temperature limit (kT<<).

Zrot=1+(2(1)+1)e-1(1+1)/kT=1+3e-2e/kT

The average energy of the system is given as follows:

Erot=-1ZrotZrotβ=-11+3e-2ββ(1+3e-2β)=-11+3e-2β(3e-2β(-2))=6e-2β1+3e-2β

Neglecting the term 3e-2βin the denominator of 6e-2β1+3e-2β,

Since the function 3e-2βapproaches to zero as βbecause e-=0.

Therefore, the average energy of the system is 6e-2β.

03

Step 3. Specific heat capacity of the system

The specific heat capacity of the system is given by,

C=ErotT=T(6e-2β)=6T(e-2/kT)=6(e-2/kT)-2k-1T2=122kT2e-2/kT=3k2kT2e-2/kT

Therefore, the heat capacity of the system in the low temperature limit is C=3k2kT2e-2/kT.

In the low temperature limit, the heat capacity of the system decreases exponentially to zero.

04

Step 4. Behavior ho heat capacity

The low and high temperature limit of Ckare plotted against the dimensionless parameter kT.

The graph is as follows,

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Most popular questions from this chapter

2. Consider a classical particle moving in a one-dimensional potential well u(x), as shown The particle is in thermal equilibrium with a reservoir at temperature T, so the probabilities of its various states are determined by Boltzmann statistics.

{a) Show that the average position of the particle is given by

where each integral is over the entire xaxis.

A one-dimensional potential well. The higher the temperature, the farther the particle will stray from the equilibrium point.

(b) If the temperature is reasonably low (but still high enough for classical mechanics to apply), the particle will spend most of its time near the bottom of the potential well. In that case we can expand u(x)in a Taylor series about the equilibrium point x0: u(x)=ux0+x-x0dudxx0+12x-x02d2udx2x0

+13!x-x03d3udx3x0+

Show that the linear term must be zero, and that truncating the series after the quadratic term results in the trivial prediction x=x0.

(c) If we keep the cubic term in the Taylor series as well, the integrals in the formula for xbecome difficult. To simplify them, assume that the cubic term is small, so its exponential can be expanded in a Taylor series (leaving the quadratic term in the exponent). Keeping only the smallest temperature-dependent term, show that in this limit x differs from zo by a term proportional to kT. Express the coefficient of this term in terms of the coefficients of the Taylor series foru(x)

(d) The interaction of noble gas atoms can be modeled using the Lennard Jones potential,

u(x)=u0x0x12-2x0x6

Sketch this function, and show that the minimum of the potential well is at x=x0, with depth u0. For argon, x0=3.9Aand u0=0.010eV. Expand the Lennard-Jones potential in a Taylor series about the equilibrium point, and use the result of part ( c) to predict the linear thermal expansion coefficient of a noble gas crystal in terms of u0. Evaluate the result numerically for argon, and compare to the measured value

α=0.0007K-1(at80K)

Consider a system of two Einstein solids, where the first "solid" contains just a single oscillator, while the second solid contains 100 oscillators. The total number of energy units in the combined system is fixed at 500. Use a computer to make a table of the multiplicity of the combined system, for each possible value of the energy of the first solid from 0 units to 20. Make a graph of the total multiplicity vs. the energy of the first solid, and discuss, in some detail, whether the shape of the graph is what you would expect. Also plot the logarithm of the total multiplicity, and discuss the shape of this graph.

At room temperature, what fraction of the nitrogen molecules in the air are moving at less than300m/s?

Use a computer to sum the exact rotational partition function numerically, and plot the result as a function ofkT. Keep enough terms in the sum to be confident that the series has converged. Show that the approximation in equation 6.31 is a bit low, and estimate by how much. Explain the discrepancy

Cold interstellar molecular clouds often contain the molecule cyanogen (CN), whose first rotational excited states have an energy of 4.7x 10-4 eV (above the ground state). There are actually three such excited states, all with the same energy. In 1941, studies of the absorption spectrum of starlight that passes | through these molecular clouds showed that for every ten CN molecules that are in the ground state, approximately three others are in the three first excited states (that is, an average of one in each of these states). To account for this data, astronomers suggested that the molecules might be in thermal equilibrium with some "reservoir" with a well-defined temperature. What is that temperature?

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