12/09/2019 Selected Solutions to McQuarrie’s Statistical Mechanics Chapter 1 | Math and Science Tricks

Math and Science Tricks

Just another WordPress.com weblog

Selected Solutions to McQuarrie’s Statistical Mechanics

Chapter 1

Problem 1-49
Maximize

with respect to each under the constraints that

Solution: Apply, first, Stirling’s approximation to , giving

But, one of the constraints states that so this gives

Then, necessarily

And the total differential is, likewise

where the other terms vanish because they are constants. Turning to the constraints, we write out
their differentials

From this, we can conclude that Equation (7

(///Users/jacoblerche/Documents/Blog/post0003_statmechhw01/post-template.html#eqwdiff)) may be
wri en

Then, applying Lagrange multipliers returns an expression as follows

https://sciencetricks.wordpress.com/2010/04/01/selected-solutions-to-mcquarries-statistical-mechanics-chapter-1/ 1/5
12/09/2019 Selected Solutions to McQuarrie’s Statistical Mechanics Chapter 1 | Math and Science Tricks

In principle, and could be picked to solve for and , but any two terms may be picked while
leaving the other terms in the series completely independent. In which case, treat all the terms as
mutually exclusive, and so each term must individually be zero. Or, for all values

So it follows that

Problem 1-50
Show that the maximum of a multinomial distribution is given when .
Solution: The multinomial coefficients are given by

Similar to the previous problem, with Lagrange multipliers applied, results in

Then, writing out the partial derivatives gives

From which we may conclude that . Hence if there are ‘s subject to the
restriction , it follows that

As required.
Problem 1-51
Use the method of undetermined multipliers to show that

subject to the condition

is a maximum when constant.

Solution: Let

https://sciencetricks.wordpress.com/2010/04/01/selected-solutions-to-mcquarries-statistical-mechanics-chapter-1/ 2/5
12/09/2019 Selected Solutions to McQuarrie’s Statistical Mechanics Chapter 1 | Math and Science Tricks

Then, applying Lagrange multipliers to the constraint gives the following relation

Taking the partial derivatives with respect to each shows that they are all equal to each other, as in
the previous problem. Hence for ‘s we have

which is a constant, as required.

Problem 1-55

Show that is an even function of .

Solution: Expanding out the binomial in the denominator gives

Then, factoring out and canceling gives

An even function is defined as satisfying the following relationship . Here, it is clear

that effecting the change of signs will leave the equation unchanged. Similarly

Again, it is clear that interchanging the signs leaves the equation the same.

Problem 1-56
The heat capacity of the Einstein model of a crystal is given by

where is the “characteristic temperature” of the crystal. Determine both the high- and low-
temperature limiting expressions for the heat capacity. Do the same thing for the Debye model of
crystals, in which

where is the Debye temperature of the crystal.

https://sciencetricks.wordpress.com/2010/04/01/selected-solutions-to-mcquarries-statistical-mechanics-chapter-1/ 3/5
12/09/2019 Selected Solutions to McQuarrie’s Statistical Mechanics Chapter 1 | Math and Science Tricks

Solution: For , ie the high temperature limit, the top exponential because its ratio in the
exponent goes to zero. The bo om one may be expanded out as a power series as for small so
only the linear terms are kept

And so in the high temperature limit, as . Similarly, if then as in Problem

(1-55) we have

Necessarily, the right most exponential vanishes. Then, the term may be neglected because
compared to for large it contributes nothing. Then,

For the Debye equation, as the upper limit of integration may be replaced with , thus

The integral, as looked up in a table of integrals, evaluates to

so all together the expression for the low temperature limit is

In the high temperature limit, assume that is small. Similar to the Einstein model, the top
exponential tends to , and the bo om exponential is expanded in a power series keeping only the
linear terms

Problem 1-57
Recognizing it as a geometric series, sum the following series in closed form:

https://sciencetricks.wordpress.com/2010/04/01/selected-solutions-to-mcquarries-statistical-mechanics-chapter-1/ 4/5
12/09/2019 Selected Solutions to McQuarrie’s Statistical Mechanics Chapter 1 | Math and Science Tricks

Compare this result to

Under what conditions are these two results the same?

Solution: The sum of a geometric series is given by

Here, and so then the sum is

The integral evaluates to

Le ing leaves . Then, equating the two leads to

So when , the two are the same.

This entry was posted on April 1, 2010 at 5:12 am and is filed under Uncategorized. You can follow
any responses to this entry through the RSS 2.0 feed. You can leave a response, or trackback from
your own site.

Create a free website or blog at WordPress.com.

Entries (RSS) and Comments (RSS).

https://sciencetricks.wordpress.com/2010/04/01/selected-solutions-to-mcquarries-statistical-mechanics-chapter-1/ 5/5