Liouville equation - equilibrium

In summary, the conversation discusses the concept of Liouville equation in a Hamiltonian system, where the volume of phase space and probability density are conserved. It also explores the idea of an isolated Hamiltonian system reaching an equilibrium state, which is a concept from thermodynamics and involves a time-independent probability distribution function. The conversation concludes that in order for the system to reach equilibrium, it needs to interact with a thermal reservoir and then be disconnected in order to deviate from the Liouville equation and reach the equilibrium value of the probability density.
  • #1
lakmus
23
1
Hi!
I have problem with uderstanding of Liouville equation. Which sais that if we have a
Hamiltonian system (energy is conserved), then the the volume of phase space is
conserved, or equivalently the probability density is conserved (the total derivative
of probability density per time is 0).
On the other hand, and isolated hamiltonian system is going to an equilibrium state,
where the probability density is the same for all state in phase space.

How can system reach the equilibrium, when the probaility density is on the develpment
trajectory conserved and at the beginning is not the same for all state?

Thaks a lot!
 
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  • #2
... isolated hamiltonian system is going to an equilibrium state,

Isolated Hamiltonian system cannot be "going to an equilibrium state".

Let the energy of such system be ##E##.

In general almost any microstate on the energy hypersurface ##E## remains accessible to the system, it is only a question of time when the system will get there.

This can be easily seen from the Liouville equation: the probability behaves as incompressible liquid, it does not accumulate in some hypothetical microstate of equilibrium (nor in a region of equilibrium) in phase space.

The concept of "equilibrium state" is a notion from thermodynamics, used to describe a body whose macroscopic description - macrostate ##S##(pressure, temperature) has a meaning and whose time variation can be neglected.

In statistical physics, knowledge of the macrostate implies probability distribution function ##\rho(q,p)## on the phase space. Since the macrostate of the body in equilibrium can be considered as time-independent, it is most natural to require that the value of ##\rho## for any microstate ##q,p## be also time-independent.

From this assumption and the Liouville theorem it follows that the Poisson bracket of ##\rho## and ##H## vanishes. This can happen if ##\rho## is a function of ##H##.

the probability density is the same for all state in phase space.

Th equilibrium value of the distribution ##\rho## is the same only for the microstates that correspond to the energy ##E##, i.e. for ##q,p## such that ##H(q,p) = E##.

How can system reach the equilibrium, when the probaility density is on the develpment
trajectory conserved and at the beginning is not the same for all state?

It is not the system what can reach the equilibrium. It is the function ##\rho(q,p)## that may reach the equilibrium value ##\rho(q,p) = \rho_0(E)##. In order to accomplish this, however, it has to evolve differently than according to the above Liouville equation, since as you have noticed, the latter preserves the initial values of density ##\rho## (it only changes ##q,p## they correspond to.)

The system has to be brought to interaction with other system (thermal reservoir) and then disconnected. During the interaction, the above Liouville equation for ##\rho## does not apply; there will be new forces due to the reservoir. As a result of these external forces, the resulting ##\rho## may get close to equilibrium value ##\rho_0(E')## for the newly acquired value of energy ##E'##.
 
  • #3
Was the above helpful? Now that I'm reading the posts again, I am not sure whether we understood each other.
 

1. What is the Liouville equation in equilibrium?

The Liouville equation is a mathematical equation that describes the time evolution of a statistical distribution in a system in equilibrium. It is used to calculate the probability of finding a particle or molecule in a particular state at a given time.

2. How is the Liouville equation derived?

The Liouville equation is derived from the principle of conservation of probability, which states that the total probability of all possible states in a system must remain constant over time. It is also based on the Hamiltonian equations of motion, which describe the dynamics of a system.

3. What is the significance of the Liouville equation in equilibrium?

The Liouville equation is significant because it provides a fundamental understanding of the behavior of particles and molecules in a system in equilibrium. It allows us to predict the probability of finding a particle in a particular state at a given time, which is crucial for many scientific applications.

4. How is the Liouville equation used in statistical mechanics?

The Liouville equation is a key tool in statistical mechanics, as it allows for the calculation of important quantities such as the entropy, free energy, and partition function of a system. These quantities are essential for understanding the thermodynamic properties of a system in equilibrium.

5. Can the Liouville equation be applied to all physical systems?

Yes, the Liouville equation can be applied to all physical systems that are in equilibrium, regardless of the type of particles or molecules present. It is a universal equation that is widely used in fields such as chemistry, physics, and biology to study the behavior of microscopic systems.

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