Derivation of Crooks's Fluctuation Theorem

In summary, the derivation of the fluctuation theorem in both Crooks's and Mansour et al.'s papers involves using a quantity ##Z## that is defined as the logarithm of the ratio of forward-time path probability to reverse-time path probability. The probability of observing a specific entropy production is then obtained by taking the ensemble average over all paths. In the next step, the authors use the delta function to pull the exponential outside the integral, which is possible due to the properties of the delta function. This leads to the fluctuation theorem, which states that the ratio of the probability of observing a specific entropy production to the probability of observing its negative value is equal to the exponential of the entropy production.
  • #1
TeethWhitener
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I'm reading through Crooks's paper:
https://journals.aps.org/pre/abstract/10.1103/PhysRevE.60.2721
as well as a review paper by Mansour et al.:
https://aip.scitation.org/doi/10.1063/1.4986600
trying to figure out their derivation of the fluctuation theorem (section II of both papers). I had a question about the math behind one specific part of the derivation. The derivation is essentially identical in both papers, but I'll use Mansour's notation.

We have a stochastic process with a forward-time path through phase space denoted ##\mathbf{X}##, and a time-reversed path ##\mathbf{\overline{X}}##. We define a quantity
$$Z(\mathbf{X}) = \ln{\frac{P(\mathbf{X})}{P(\mathbf{\overline{X}})}}$$
where ##P(\mathbf{X})## is the probability density of ##\mathbf{X}##. Then ##Z## is just the logarithm of the ratio of the forward-time path probability to the reverse-time path probability (in thermodynamic terms, this is related to the entropy change of a process). To find the probability that we will observe a particular entropy production, ##\zeta <Z<\zeta +d\zeta##, denoted ##P(\zeta)d\zeta##, we take the ensemble average ##\langle\delta(\zeta-Z(\mathbf{X}))\rangle## over all paths:
$$P(\zeta)=\int{d[\mathbf{X}]\delta(\zeta-Z(\mathbf{X}))P(\mathbf{X})}$$
where ##d[\mathbf{X}]=d[\mathbf{\overline{X}}]## is a suitable path integral measure and ##\delta(\zeta-Z(\mathbf{X}))## is the Dirac delta function. Then we multiply by ##\frac{P(\mathbf{\overline{X}})}{P(\mathbf{\overline{X}})}## and use the definition of ##Z## to get:
$$P(\zeta)=\int{d[\mathbf{X}]\delta(\zeta-Z(\mathbf{X}))P(\mathbf{\overline{X}})}\exp[Z(\mathbf{X})]$$
This part is fine. The next part is where I'm stumped. The authors use the delta function to pull the exponential outside the integral:
$$\int{d[\mathbf{X}]\delta(\zeta-Z(\mathbf{X}))P(\mathbf{\overline{X}})}\exp[Z(\mathbf{X})]=\exp(\zeta)\int{d[\mathbf{X}]\delta(\zeta-Z(\mathbf{X}))P(\mathbf{\overline{X}})} $$
I don't understand how they can pull the exponential out without getting rid of the integral altogether. I'm familiar with the delta function's use as:
$$\int f(x)\delta(x-\tau) dx =f(\tau)$$
but I've never seen a case where you can use the delta function on only one piece of an integrand, like they're doing above. Is this some quirk of delta functions with path integrals? Or am I missing something obvious?

Any help would be great, thanks!
 
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  • #2
Oh wait a second, is this just because ##\int {\delta(x)dx} = 1##? So that ##\int {f(x)\delta(x-\tau)dx} = f(\tau)\int {\delta(x-\tau)dx} ##? Man I'd feel really dumb if that were the case.

Edit:
So is it true in general that ##\int {f(x)g(x)\delta(x-\tau)dx} = f(\tau)\int {g(x)\delta(x-\tau)dx}##?
 
  • #3
TeethWhitener said:
Oh wait a second, is this just because ##\int {\delta(x)dx} = 1##? So that ##\int {f(x)\delta(x-\tau)dx} = f(\tau)\int {\delta(x-\tau)dx} ##? Man I'd feel really dumb if that were the case.

Edit:
So is it true in general that ##\int {f(x)g(x)\delta(x-\tau)dx} = f(\tau)\int {g(x)\delta(x-\tau)dx}##?
I should preface: that paper and your OP are beyond me.
But I can say this much: you can go a step farther;
$$\int F(x)\delta (x-\tau)dx = F(\tau)$$
Where ##\delta## is the Dirac delta function.
This of course includes the case where F(x) = f(x)g(x)
(Also, this is assuming ##\tau## is in the interval of integration.)
This is partly because (like you said) ##\int \delta (x)dx=1## , but of course it wouldn’t be true for any function ##\delta## which satisfies that equation; the key detail is that ##\delta(x-\tau)## is zero everywhere except at ##x=\tau##

Edit:
Oops, I just noticed you said you’re familiar with this in the OP, sorry! (I glossed over it once I got lost.)

What you said is also true:
$$\int f(x)g(x)\delta (x-\tau)dx = f(\tau)\int g(x)\delta (x-\tau)dx $$
Because both sides simplify to ##f(\tau)g(\tau)##

Not sure why that would be useful... but it’s indeed true.
 
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  • #4
Hiero said:
Not sure why that would be useful... but it’s indeed true.
Thanks for your help. It’s useful because after the variable transformation ##\mathbf{X}\rightarrow\mathbf{\overline{X}}##, you get:
$$\exp (\zeta) \int {d[\mathbf{X}] \delta(\zeta -Z(\mathbf{X}))P(\mathbf{\overline{X}}) }= \exp (\zeta) \int {d[\mathbf{\overline{X}}] \delta(\zeta +Z(\mathbf{\overline{X}}))P(\mathbf{\overline{X}}) }= \exp(\zeta)P(- \zeta)$$
from the previous definition of ##P(\zeta)##. This gives the fluctuation theorem immediately:
$$\frac{P(\zeta)}{P(-\zeta)}=\exp(\zeta)$$
 

1. What is Crooks's Fluctuation Theorem?

Crooks's Fluctuation Theorem is a fundamental principle in statistical mechanics that relates the probability of observing a certain amount of fluctuation in a thermodynamic system to the probability of observing the reverse fluctuation. It is applicable to systems that are far from equilibrium and provides a mathematical framework for understanding the behavior of these systems.

2. How was Crooks's Fluctuation Theorem derived?

Crooks's Fluctuation Theorem was derived by physicist Gavin Crooks in 1998. He used the principles of statistical mechanics and the concept of entropy to mathematically prove the relationship between the forward and reverse fluctuations in a system.

3. What is the significance of Crooks's Fluctuation Theorem?

Crooks's Fluctuation Theorem has significant implications for our understanding of thermodynamic systems. It provides a theoretical basis for predicting the behavior of systems that are far from equilibrium, which is crucial in many fields of science, including chemistry, biology, and physics.

4. How is Crooks's Fluctuation Theorem applied in research?

Crooks's Fluctuation Theorem has been applied in various research areas, including nanoscience, biophysics, and chemical physics. It has been used to study the behavior of small systems, such as single molecules or nanoparticles, and to understand the thermodynamics of biological processes.

5. Are there any limitations to Crooks's Fluctuation Theorem?

While Crooks's Fluctuation Theorem has been widely accepted and applied in research, it does have some limitations. It is based on certain assumptions, such as the system being in thermal equilibrium, and may not accurately describe systems that are highly non-equilibrium. Additionally, it is only applicable to systems that can be described by classical mechanics and does not take into account quantum effects.

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