Statistical physics : Irreversibility

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Discussion Overview

The discussion revolves around the concept of irreversibility in statistical physics, particularly in relation to single or few particle systems. Participants explore the implications of irreversibility, entropy, and the behavior of hydrogen atoms transitioning between energy states, referencing various theoretical frameworks and interpretations.

Discussion Character

  • Exploratory
  • Debate/contested
  • Technical explanation
  • Conceptual clarification

Main Points Raised

  • Some participants question the validity of the concept of irreversibility when considering one or few particle systems, referencing the assumption of increasing length scales in interactions.
  • One participant cites Feynman's explanation regarding the transition of a hydrogen atom from an excited to a ground state, suggesting that this process is more probable due to entropy considerations.
  • Another participant challenges the assertion that a hydrogen atom only goes from excited to ground state, noting that it can also transition in the opposite direction.
  • Some participants argue that the concept of temperature and entropy cannot be applied to single or few particle systems, emphasizing that statistical mechanics requires a larger number of particles for meaningful definitions.
  • Others propose that temperature can be defined for a single particle if it is coupled to a heat bath, referencing ergodicity and average kinetic energy in statistical mechanics.
  • There is mention of the H theorem and its relation to entropy increase, which is derived from the unitarity of the S matrix and assumptions about molecular chaos.
  • Participants discuss the implications of tracking every particle at the atomic level, with some asserting that most processes are time reversible, while others seek examples of irreversible processes in statistical mechanics.

Areas of Agreement / Disagreement

Participants express disagreement on the applicability of irreversibility and the definitions of temperature and entropy in single particle systems. Multiple competing views remain regarding the behavior of hydrogen atoms and the foundational principles of statistical mechanics.

Contextual Notes

Limitations include the dependence on definitions of temperature and entropy, as well as the assumptions regarding interactions in particle systems. The discussion does not resolve the complexities surrounding these concepts.

dontknow
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TL;DR
The Entropy of an isolated always increases.
I was reading mehran kardar (books and lectures) it says the concept of irreversibility comes from an assumption (in which we increase the length scale by interaction disctance between two particles).
So My question is the concept of irreversibility is still valid in the case of 1 particle.

Let's take an example from Feynman 2nd volume; A hydrogen atom going from excited to ground state is more probable thing to happen than a de-excited electron get excited by a photon. His explanation is that for an excited state initially entropy is low because photon (in final state) is something that is wandering in different direction so there is an increase in entropy.

Coming back to question where does the explanation for irreversibility come for the case of 1 or few particle system.
 
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dontknow said:
A hydrogen atom always goes from excited to ground state, not the other way.
Hmm, that doesn't seem right. A hydrogen atom clearly can go from the ground state to the excited state too.
 
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dontknow said:
Coming back to question where does the explanation for irreversibility come for the case of 1 or few particle system.

The single atom is interacting with many other things that are not explicitly mentioned, such as the quantum state of the electromagnetic field surrounding the atom. The background electromagnetic field can provide a thermal bath for the atom.

The background section (first paragraph) of https://arxiv.org/abs/1510.04745v1 has some related references.

Chapter 3 of https://www.uibk.ac.at/th-physik/cqed/theses/bachelorthesis_kruckenhauser_andreas.pdf models spontaneous emission by coupling the atom to the background electromagnetic field.
 
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dontknow said:
Summary:: The Entropy of an isolated always increases.
Coming back to question where does the explanation for irreversibility come for the case of 1 or few particle system.

Maybe, Feynman's reasoning can be easier understood when one conceptually explains “entropy” qualitatively in the following way:

The second law of thermodynamics says that energy of all kinds in our material world disperses or spreads out if it is not hindered from doing so. Entropy is the quantitative measure of that kind of spontaneous process: how much energy has ‘flowed’ from being localized to becoming more widely spread out (at a specific temperature). [Quotation marks by LJ]

Frank L. Lambert in “Entropy Is Simple — If We Avoid The Briar Patches!” (http://entropysimple.oxy.edu/content.htm#increase)

Thermodynamic processes entail spatial redistributions of internal energies, namely, the spatial spreading of energy. Thermal equilibrium is reached when energy has spread maximally; i.e., energy is distributed equitably and entropy is maximized.

Harvey S. Leff in “Removing the Mystery of Entropy and Thermodynamics – Part I” (Phys. Teach. 50, 28 (2012))

Feynman (in “Feynman lectures Vol. III”, Chapter 7.1) puts it in the following way:

Why does an atom radiate light? The answer has to do with entropy. When the energy is in the electromagnetic field, there are so many different ways it can be—so many different places where it can wander—that if we look for the equilibrium condition, we find that in the most probable situation the field is excited with a photon, and the atom is de-excited. It takes a very long time for the photon to come back and find that it can knock the atom back up again.
 
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The whole subject of thermodynamics including the 2nd law, is based on statistical mechanics. You can't apply statistics to 1 or 2 particles. You can't define temperature or entropy for 1 or 2 particles.

For example, what is the temperature of a free electron? There is no answer, the concept of temperature does not apply to a single particle.

Indeed, at the atomic level where we track every particle, almost all (not all but almost all) are time reversible.
 
Dale said:
Hmm, that doesn't seem right. A hydrogen atom clearly can go from the ground state to the excited state too.
Indeed, and in equilibrium the rate of excitation is the same as that of the relaxation.

The H theorem (increase of entropy) follows from the unitarity of the S matrix and Boltzmann's "molecular-chaos assumption" to truncate the BBGKY hierarchy in the usual way by approximating the two-particle phase-space distribution function with the product of the corresponding single-particle distribution functions.
 
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anorlunda said:
You can't define temperature or entropy for 1 or 2 particles.
...
There is no answer, the concept of temperature does not apply to a single particle.

For sure?
What about the average over time (ergodicity)?
In statistical mechanics temperature is an average kinetic energy.
 
rentier said:
For sure?
What about the average over time (ergodicity)?
In statistical mechanics temperature is an average kinetic energy.
Then you don't have a single particle, but an individual particle interacting with a reservoir.
 
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rentier said:
For sure?
What about the average over time (ergodicity)?
In statistical mechanics temperature is an average kinetic energy.
Sure, you can define temperature for a single particle coupled to a heat bath. Look for Fokker-Planck and/or Langevin equation.
 
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anorlunda said:
Indeed, at the atomic level where we track every particle, almost all (not all but almost all) are time reversible.

What is an example for _not_ reversible? (in statistical mechanics, not quants)
 

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