Increasing entropy vs groundstate

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Discussion Overview

The discussion revolves around the relationship between entropy and the ground state of atoms and molecules. Participants explore how these concepts interact, particularly in the context of isolated systems versus those in thermal contact with their environment. The scope includes theoretical considerations of thermodynamics and statistical mechanics.

Discussion Character

  • Exploratory
  • Debate/contested
  • Technical explanation

Main Points Raised

  • Some participants assert that atoms and molecules tend to occupy their ground state, which is the most probable state, while entropy in an isolated system is said to always increase.
  • One participant introduces the idea of a negative entropy source, such as the Sun, suggesting that the perception of order and chaos may depend on human pattern recognition rather than universal properties.
  • Another participant clarifies that the statement about entropy always increasing should be interpreted as it "practically never decreasing," emphasizing the limited ways for an atom to be in an excited state compared to the arrangements possible when it decays.
  • It is noted that when an atom transitions to its ground state, it emits a photon, which contributes to the overall entropy, thus maintaining the principle that total entropy increases.
  • One participant argues that atoms only prefer the ground state when not isolated, and in thermal contact with the environment, all states of the combined system are equally likely, linking this to the concept of free energy minimization.

Areas of Agreement / Disagreement

Participants express differing views on the implications of entropy in isolated versus non-isolated systems. There is no consensus on how to reconcile the concepts of ground state preference and entropy increase, indicating ongoing debate and exploration of the topic.

Contextual Notes

Some limitations include the dependence on definitions of isolated versus non-isolated systems and the assumptions regarding the behavior of atoms in different contexts. The discussion does not resolve the mathematical or conceptual intricacies involved.

Jim Kata
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Atoms and molecules like to be in their ground state, that is its most probabilistic for them to be in the ground state, but the entropy of an isolated system is always increasing. Which implies, to my understanding, all states should be equally likely. There is something I'm definitely missing. How do I reconcile these two concepts?
 
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Here's an interesting link on the concept of a negative entropy source (the Sun):

http://www.digital-recordings.com/publ/publife.html

I recall a similar description in the book A Brief History of Time.

My problem with entropy theory is that, if my brain recognizes a pattern, I call it "order" and if it doesn't, I call it "chaos" or "disorder." So the line between the two is perhaps not a property of the universe, but perhaps a natural limit on the power of pattern recognition.
 
Jim Kata said:
Atoms and molecules like to be in their ground state, that is its most probabilistic for them to be in the ground state, but the entropy of an isolated system is always increasing. Which implies, to my understanding, all states should be equally likely. There is something I'm definitely missing. How do I reconcile these two concepts?

Not "always increasing" just "practically never decreasing".

Consider: there are only a few "ways" for an atom (with a particular amount of energy) to be in an excited state. This system can decay into a photon and a ground state atom, and then there will be an infinite range of "ways" that those two could be arranged. (The thermodynamic microstates correspond to all those "ways"/arrangements of the entire system, not to the atomic electron states by themselves; the latter doesn't even correspond to a closed system.)
 
Last edited:
Jim Kata said:
Atoms and molecules like to be in their ground state, that is its most probabilistic for them to be in the ground state, but the entropy of an isolated system is always increasing. Which implies, to my understanding, all states should be equally likely. There is something I'm definitely missing. How do I reconcile these two concepts?
When an atom drops into its ground state, it gives off a photon. The entropy of the photon makes up for the entropy loss of the atom itself, so that the total entropy always increases. Remember that once the atom gives off that photon, it's not isolated.

(cesiumfrog was right, though, it technically is "almost never decreases" rather than "always increases." But the probability of seeing entropy decrease in a real system is astronomically low, i.e. we have every reason to expect that it's never happened.)
 
Jim Kata said:
Atoms and molecules like to be in their ground state, that is its most probabilistic for them to be in the ground state, but the entropy of an isolated system is always increasing. Which implies, to my understanding, all states should be equally likely. There is something I'm definitely missing. How do I reconcile these two concepts?
Atoms and molecules only like to be in the ground state, when their are not an isolated system. You are right that if they were isolated, then all states would be equally likely. However atoms are in thermal contact with the environment. All state of the combined system environment+atom are indeed equally likely. One can derive that this is equivalent to saying that the free energy of the atoms is the smallest possible.
 

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