02:21
@imbAF A free particle of specific momentum is a stationary state but not bound. A time dependent Hamiltonian can have a bound state that is not stationary. It is not even clear that time dependent Hamiltonians allow for a sensible definition of what stationary states.
@Obliv You have already taken a step into semi-classical, because you are doing statistical thermodynamics. If you consider the microcanonical ensemble in classical mechanics, your integral over the entire phase space, even if constrained to a specific energy, is an infinite quantity. You need even just a bit of semi-classicalness to have that be finite, and then the usual mathematics would work.
@SillyGoose Minor nitpick: If you are assuming Boltzmann stats, then you are assuming canonical ensemble, not grand canonical.
@Obliv Do you begin to realise that your education in statistical thermodynamics is missing fundamental components? There are plenty of good textbooks that cover these conceptually important issues. I mean, what would a physics textbook that fails to cover the physics concepts relevant to a topic be of use for?
@SillyGoose Please don't invent stuff like mesostates; not least because things like that are almost certain to be used somewhere else in physics. Also, your definition is worded in a way that is trying to be general, but fails at it, because, imagine your AB to only be allowing thermal exchange. Then it cannot be in equilibrium by your definition, because it is not in mechanical and chemical equilibrium at the same time as thermal equilibrium.
@SillyGoose He isn't ready for postgraduate statistical thermodynamics yet...
@imbAF You can. The pathway is more sensible from MCE to CE to GCE. When going backwards, the results become much more approximate, with weird things like the fluctuation in E when you are meant to have already fixed E, say. It is a consequence of that fact that when we start directly with CE and GCE, things are assumed to be probabilistically distributed, so nothing is specified.
@imbAF The difference is negligible in the thermodynamic limit, by definition. However, it can be extremely visible when the quantum system being considered is small.
@SillyGoose It is very much encouraged. Not very useful to go back to sticks and stones when you already have rockets and lasers and drones.
@imbAF No, your conception of that is actually wrong. What we are doing is actually really first imagining that the system under consideration is infinitely large, that the boundary terms are gone. This is needed to throw away nuisances like surface tension. Then you mathematically and theoretically imagine a mathematical surface corresponding to the same size and shape as the experiment's volume, and try to match the experiment's results with that of this theoretical construct.