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Stirling approximation revisited The Stirling approximation is useful in a variety of differ. ent settings. The goal of the present problem is to work through a more sophisticated treatment of this approximation than the simple heuristic argument given in the chapter. Our task is to find useful representations of \(n\) then since terms of the form in \(n\) arise often in reasoning about entropy. (a) Begin by showing that $$n !=\int_{0}^{\infty} x^{n} \mathrm{e}^{-x} \mathrm{d} x$$ To demonstrate this, use repeated integration by parts. In particular, demonstrate the recurrence relation $$\int_{0}^{\infty} x^{n} e^{-x} d x=n \int_{0}^{\infty} x^{n-1} e^{-x} d x$$ and then argue that repeated application of this relation Ieads to the desired result. (b) Make plots of the integrand \(x^{n} e^{-x}\) for various values of \(n\) and observe the peak width and height of this inter. grand. We are interested now in finding the value of \(x\) for which this function is a maximum. The idea is that we will then expand about that maximum. To carry out this step, consider \(\ln \left(x^{\pi} e^{-x}\right)\) and find its maximum - argue why it is acceptable to use the logarithm of the original function as a surrogate for the function itself-that is, show that the maxima of both the function and its logarithm are at the same \(x\). Also, argue why it might be a good idea to use the logarithm of the integrand rather than the integrand itself as the basis of our analysis. Call the value of \(x\) for which this function is maximized \(x_{0}\). Now expand the logarithm about \(x_{0},\) In particular, examine $$\ln \left|\left(x_{0}+b\right)^{n} e^{-\left(x_{0}+b\right)}\right|=n \ln \left(x_{0}+d\right)-\left(x_{0}+8\right)$$ and expand to second order in \(\delta\), Exponentiate your result and you should now have an approximation to the orig. inal integrand which ts good in the neighborhood of \(x_{0}\) Plug this back into the integral (be careful with limits of Integration) and by showing that it is acceptable to send the lower limit of integration to \(-\infty,\) show that $$n ! \Leftrightarrow n^{\pi} \mathrm{e}^{-n} \int_{-\infty}^{\infty} \mathrm{e}^{-g^{2} / 2 n} \mathrm{d} \delta$$ Evaluate the integral and show that in this approximation $$n !=n^{n} e^{-n}(2 \pi n)^{1 / 2}$$ Also, take the logarithm of this result and make an argument as to why most of the time we can get away with dropping the \((2 \pi n)^{1 / 2}\) term.

Short Answer

Expert verified
Finally after performing all the steps, it is found that the Stirling’s approximation for \(n!\) is \(n!=n^n e^{-n}(2 \pi n)^{1 / 2}\). Furthermore, by taking logarithm to this result, it is seen that the \((2\pi n)^{1 / 2}\) term often can be neglected due to its slower growth rate compared to other terms.

Step by step solution

01

Recursive integral representation

We are asked to demonstrate that \(n! = \int_{0}^{\infty} x^n e^{-x} dx\). We start off using integration by parts with \(u=x^n\), \(v=e^{-x}\), \(dv=-e^{-x} dx\), and \(du=n x^{n-1} dx\). After performing the integration by parts, we find a relation that can be recursively applied since after each integration by parts operation, the power of \(x\) in the integrand decreases by one. This provides an equivalent representation of \(n!\), and the base case corresponds to \(0!=\int_{0}^{\infty} x^0 e^{-x} dx\) which evaluates to 1, verifying our start point.
02

Examine properties of integrand

The next objective is to examine \(x^n e^{-x}\) for various values of \(n\), focusing on its peak width and height. Plot this function for different \(n\)'s to visually understand its behaviour. Find the maximum of this function or equivalently the maximum of \(\ln \left(x^n e^{-x}\right)\) which would be at the same \(x\) value. It is easier to work with logarithm of the function, because logarithm converts the product of functions to their sum, simplifying the derivative computation for finding maximum.
03

Expansion around the maximum

Call the value of \(x\) for which the logarithm function is maximized \(x_0\). This function is now expanded about \(x_0\). Consider the function \(\ln |(x_0+\delta)^n e^{-(x_0+\delta)}|=n \ln (x_0+\delta)-(x_0+\delta)\). This function should be expanded to the second order in \(\delta\). Hence, the approximation to the original integrand would be valid around \(x_0\).
04

Integral Evaluation

Substituting this approximation back into integral would be the next step. One should check the conditions under which the lower limit of integration can be extended to \(-\infty\). The eventual goal is to show that \(n ! \Leftrightarrow n^n e^{-n} \int_{-\infty}^{\infty} e^{-\delta^{2} / 2n} d\delta\). Evaluate this integral and achieve the Stirling’s approximation for \(n!\).
05

Simplify Result

The final approximated result would be \(n!=n^n e^{-n}(2 \pi n)^{1 / 2}\). Take the logarithm of this result and analyse why most of the times we can ignore the \((2\pi n)^{1 / 2}\) term.

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Integration by Parts
Integration by parts is a powerful technique used in calculus to evaluate more complex integrals by decreasing the degree of the function inside the integral. This technique is based on the product rule of differentiation and can be summarized with the formula:
\[ \int u \ dv = uv - \int v \ du \]
This means, if you have a product of two functions, you can differentiate one part (the function designated as \(u\)) and integrate the other part (the function designated as \(dv\)).
In the exercise for demonstrating that the factorial \(n! = \int_{0}^{\infty} x^n e^{-x} dx\), integration by parts is used repeatedly. The choices made are \(u = x^n\) and \(dv = e^{-x} dx\), which transforms the integral and reduces the power of \(x\). Each repetition of these steps transforms the integral into a simpler form until it equals one at the base case (for \(0!\)).
Understanding the mechanism of integration by parts helps to simplify complex expressions, particularly when a direct approach to integration is not apparent.
Maximum of a Function
Finding the maximum of a function is a fundamental calculus problem often solved by taking the derivative of the function and setting it to zero. This identifies the critical points, which can then be analyzed to determine if they are maxima, minima, or saddle points.
In the context of the exercise, the goal is to find the maximum value of the function \(x^n e^{-x}\). By taking the derivative with respect to \(x\) and setting it equal to zero, the critical points are identified. However, instead of working directly with the function, its logarithm is used, thanks to the property of logarithms that makes derivatives easier to handle.
This substitution is valid because the logarithm function has the same critical points as the original function when dealing with positive values of \(x\). Calculating the maximum using \(\ln(x^n e^{-x})\) simplifies the problem, turning the multiplication into addition, which substantially eases finding the derivative and thus the critical points.
Logarithmic Expansion
Logarithmic expansion is a technique that simplifies the handling of functions by expanding around a point, usually to make the solution of a problem more manageable.
In this exercise, after finding the point \(x_0\) where \(\ln(x^n e^{-x})\) reaches its maximum, an expansion around this point simplifies the function for further analysis.
This process typically involves finding the first few terms in the Taylor series expansion, capitalizing on the fact that near a maximum or minimum, many terms of the series become small and can be ignored. For example, the function is expanded in the neighborhood of \(x_0\), resulting in terms \(n \ln(x_0 + \delta) - (x_0 + \delta)\).
Higher order terms in \(\delta\) (which represents small deviations from \(x_0\)) can be ignored, allowing the expression to be simplified into an approximated form that's easier to integrate, particularly when applied to the specific integral involved in the Stirling approximation.
Integral Evaluation
Evaluating integrals, especially those resulting from approximation, is an essential skill in mathematical methods used for analyzing and approximating functions.
In the context of this exercise, once the original integrand is approximated using logarithmic expansion, the integral is re-evaluated. This requires making certain assumptions, such as extending the lower limit of integration to \(-\infty\), which is valid under the expansion context.
The specific goal in this step is to arrive at the Gaussian integral form which is known to be \(\sqrt{2 \pi} \) when evaluated from \(-\infty\) to \(\infty\). Applying this evaluation leads you to the Stirling's approximation formula for factorial:
\[ n! = n^n e^{-n} (2 \pi n)^{1/2} \]
The factorial, originally a product, transforms into an exponential function with adjustments from the integral evaluation, providing a powerful approximation used in many fields including statistics and physics.

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Most popular questions from this chapter

Molecular driving forces In Section 5.5 .2 we showed that entropy maximization leads to our intuitive ideas about equilibrium. However. that discussion can be extended to reveal the direction of spontaneous processes. In particular, during any spontaneous process, we know that the entropy will increase. Use this fact in the form of the statement that (12,2) \(\left.\mu_{1}\right) d N_{1} \geq 0\) to deduce the role of differences in chemical potential as a "driving force" for mass transport, If \(\mu_{2}>\mu_{1},\) in which direction will particles flow? Make analogous arguments for the fiow of energy and changes in volume.

A feeling for the numbers: covalent bonds (a) Based on a typical bond energy of \(150 \mathrm{kg}\) T and a typical bond length of 1.5 A. use dimensional analysis to estimate the frequency of vibration of covalent bonds. (b) Assume that the Lennard-Jones potential given by $$V(r)=\frac{a}{r^{12}}-\frac{b}{r^{6}}$$ describes a covalent bond (though real covalent bonds are more appropriately described by alternatives such as the Morse potential which are not as convenient analytically). Using the typical bond energy as the depth of the poten. tial and the typical bond length as its equilibrium position find the parameters \(a\) and \(b\), Do a Taylor expansion around this equilibrium position to determine the effective spring constant and the resulting typical frequency of vibration. (c) Based on your results from (a) and (b), estimate the time step required to do a classical mechanical simulation of protein dynamics.

A feeling for the numbers: comparing multiplicities Boltzmann's equation for the entropy (eqn 5.29 ) tells us that the entropy difference between a gas and a liquid is given by \(S_{\text {gar }}-S_{\text {liquid }}=k_{E} \ln \frac{W_{\text {Qas }}}{W_{\text {llavid }}}\) From the macroscopic definition of entropy as \(\mathrm{d} S=\mathrm{d} Q / \mathrm{T}\) we can make an estimate of the ratios of multiplicities by noting that boiling of water takes place at fixed \(T\) at 373 K. (a) Consider a cubic centimeter of water and use the result that the heat needed to boil water (the latent heat of vaporIzation) is given by \(Q_{\text {weviration }}=40.66 \mathrm{kJ} / \mathrm{mol}\) (at \(100^{\circ} \mathrm{C}\) ) to estimate the ratio of multiplicities of water and water vapor for this number of molecules. Write your result as 10 to some power. If we think of multiplicities in terms of an ideal gas at fixed \(T,\) then $$\frac{w_{1}}{W_{2}}=\left(\frac{V_{1}}{V_{2}}\right)^{N}$$ What volume change would one need to account for the liquid/vapor multiplicity ratio? Does this make sense? (b) In the chapter we discussed the Stirling approximation and the fact that our results are incredibly tolerant of error. Let us pursue that in more detail. We have found that the typical types of multiplicities for a system like a gas are of the order of \(W \approx \exp \left(10^{25}\right) .\) Now, let us say we are off by a factor of \(10^{1000}\) in our estimate of the multiplicities, namely, \(W=10^{1000} \exp \left(10^{25}\right) .\) Show that the difference in our evaluation of the entropy is utterly negligible whether we use the first or second of these results for the multiplicity. This is the error tolerance that permits us to use the Stirling approximation so casually!

Counting and diffusion In this chapter, we began practising with counting arguments. One of the ways we will use counting arguments is in thinking about diffusive trajectories. Consider eight particles, four are black and four are white. Four particles can fit left of a permeable membrane and four can fit right of the membrane. Imagine that due to randorn motion of the particles every arrangement of the eight particles is equally likely. Some possible arrangements are: BBBBIWWWW, BBBW|BWWW. WBWBIWBWB: the membrane position is denoted by (a) How many different arrangements are there? (b) Calculate the probability of having all four black particles on the left of the permeable membrane. What is the probability of having one white particle and three black particles on the left of the membrane. Finally, calculate the probability that two white and two black particles are left of the membrane. Compare these three probabilities. Which arrangement is most likely? (c) Imagine that in one time instant a random particle from the left-hand side exchanges places with a random particle on the right-hand side. Starting with three black particles and one white particle on the left of the mem brane, compute the probability that after one time instant there are four black particles on the left. What is the probability that there are two black and two white particles on the left, after that same time instant? Which is the more likely scenario of the two? (Adapted from example 2.3 from \(\mathrm{K}\). Dill and \(\mathrm{S}\). Bromberg. Molecular Driving Forces, New York, Garland Science, 2003.5

Energy cost of macro molecular synthesis In this problem you will determine the bio synthetic cost of generating the amino acid serine from glucose used as food. The bio synthetic costs of all the amino acids are given in Table \(5.1,\) and now you will get a first-hand sense of how to obtain those values, Visit the website "ecocyc.org" and find the metabolic pathways for serine synthesis and glycolysis. The starting molecule of the ser. Ine synthesis pathway is an intermediate in glycolysis. How many molecules of glucose must be taken up to provide the carbon skeleton used to make serine? Draw the biochemical pathway starting with glucose and ending in serine, labeling the energy-requiring and energy Eenerating steps. How many molecules of ATP are consumed and created along the way? How many reducing equivalents of NADH and NADPH are consumed or created along the way? In order to answer this question com pletely you may need to consider a few other pathways as well. For example, it is likely that the displayed glycolysis pathway does not actually start with glucose. To get glucose- 6 -phosphate from glucose requires 1 ATP. One of the steps in the serine synthesis pathway is coupled to a conversion of \(L\) -glutamate to 2 -ketoglutarate. You will have to look up the "glutamate biosynthesis III" pathway to determine the cost of regenerating \(L\) -glutamate from 2-ketoglutarate. Assuming that each NADH or NADPH is equivalent to 2 ATP, which is a reasonable conversion fac tor for bacteria, what is the net energy cost to synthesize one molecule of serine in units of \(\mathrm{ATP}\) and units of \(k_{B} T ?\)

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