Question about the Hamiltonian and the third law of thermodynamics

In summary, the third law of quantum mechanics states that at absolute zero temperature, a system has zero entropy, meaning there is only one microstate configuration that can produce the given macrostate. This is because the positions of quantum particles are indistinguishable and shuffling them does not result in a new microstate. However, it is possible to change the positions of the particles to maintain absolute zero temperature, and this may suggest that there is only one stable solution to the spatial configuration of particles at this temperature.
  • #1
floyd0117
6
0
The third law of quantum mechanics states that a system at absolute zero temperature has zero entropy. Entropy can be conceived as an expression of the number of possible microstates that can produce an identical macrostate. At zero entropy, there should be exactly *one* microstate configuration that can produce the macrostate in question.

For instance, take the following macrostate as an example,

- T = 0
- V = v, dV/dt = 0
- P = p, dP/dt = 0

Indeed the microstate describing this macrostate is unique in quadratic terms (the momentum of every particle must be zero). But it does not seem to be unique in the first-order terms - I can shuffle the positions of the particles all I want and keep producing the same macrostate.

So, by formal definition, is entropy only affected by quadratic and higher order terms of the Hamiltonian of the N particles contributing to the macrostate?
 
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  • #2
floyd0117 said:
I can shuffle the positions of the particles all I want and keep producing the same macrostate.
Quantum particles are indistinguishable, so shuffling positions gives the same microstate.
 
  • #3
Dale said:
Quantum particles are indistinguishable, so shuffling positions gives the same microstate.
Okay sure, I should have said to actually change the positions rather than "shuffling" them, so that each position is new and was not realized in the previous configuration.

Edit: could it be that there is in fact only one stable solution to the spatial configuration of a set of particles at T=0? And therefore I cannot change the positions and actually maintain absolute zero temperature?
 
Last edited:

Related to Question about the Hamiltonian and the third law of thermodynamics

1. What is the Hamiltonian in thermodynamics?

The Hamiltonian is a mathematical function that represents the total energy of a system in thermodynamics. It takes into account the kinetic and potential energies of all the particles in the system.

2. How is the Hamiltonian related to the third law of thermodynamics?

The third law of thermodynamics states that the entropy of a pure crystal at absolute zero temperature is zero. The Hamiltonian is used to calculate the entropy of a system, and when the temperature reaches absolute zero, the Hamiltonian becomes constant and the entropy is zero, in accordance with the third law.

3. Can the Hamiltonian be used to determine the state of a system?

Yes, the Hamiltonian is a function of the state variables of a system, such as temperature, pressure, and volume. By solving the Hamiltonian equations, one can determine the state of a system at a given point in time.

4. Is the Hamiltonian conserved in all thermodynamic processes?

No, the Hamiltonian is only conserved in adiabatic processes, where no heat is exchanged between the system and its surroundings. In other thermodynamic processes, the Hamiltonian may change due to the exchange of heat and work.

5. How is the Hamiltonian used in practical applications of thermodynamics?

The Hamiltonian is used in various practical applications, such as in the design and optimization of thermodynamic systems and processes. It is also used in the analysis of phase transitions and in the calculation of thermodynamic properties of materials.

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