Thermal equilibrium: In a system which is in thermal equilibrium, the long-time averages of the macroscopic quantities are time-independent (e.g. temperature, pressure, chemical potential).The probability distribution from which the average is taken is also timeindependent. Micro-states: If the generalized coordinate and momenta of each particle maybe determined, then that would be called a micro-state.On the other hand total momenta would be a macro-state of the system. Accessible Micro-states: If the total energy of the system is E, no individual particle can have a kinetic energy greater than that.Therefore some micro-states are not accessible to the system. If we increase E, then more micro-states will be accessible to the particle. Now, how all microscopic states become equally likely is an area of active current research. There is no general proof, because although this assumption is an extremely successful one in statistical mechanics, it doesn’t always happen. A lot of modern research tests its limits: like, if you begin with an isolated system in a highly non-equilibrium state, will it actually evolve such that a description in terms of something remarkable like a micro-canonical ensemble eventually becomes appropriate ?
Thermal equilibrium: In a system which is in thermal equilibrium, the long-time averages of the macroscopic quantities are time-independent (e.g. temperature, pressure, chemical potential).The probability distribution from which the average is taken is also timeindependent. Micro-states: If the generalized coordinate and momenta of each particle maybe determined, then that would be called a micro-state.On the other hand total momenta would be a macro-state of the system. Accessible Micro-states: If the total energy of the system is E, no individual particle can have a kinetic energy greater than that.Therefore some micro-states are not accessible to the system. If we increase E, then more micro-states will be accessible to the particle. Now, how all microscopic states become equally likely is an area of active current research. There is no general proof, because although this assumption is an extremely successful one in statistical mechanics, it doesn’t always happen. A lot of modern research tests its limits: like, if you begin with an isolated system in a highly non-equilibrium state, will it actually evolve such that a description in terms of something remarkable like a micro-canonical ensemble eventually becomes appropriate ?
We study the nature of and approach to thermal equilibrium in isolated quantum systems. An individual isolated macroscopic quantum system in a pure or mixed state is regarded as being in thermal equilibrium if all macroscopic observables assume rather sharply the values obtained from thermodynamics. Of such a system (or state) we say that it is in macroscopic thermal equilibrium (MATE). A stronger requirement than MATE is that even microscopic observables (i.e., ones referring to a small subsystem) have a probability distribution in agreement with that obtained from the micro‐canonical, or equivalently the canonical, ensemble for the whole system. Of such a system we say that it is in microscopic thermal equilibrium (MITE). The distinction between MITE and MATE is particularly relevant for systems with many‐body localization (MBL) for which the energy eigenfuctions fail to be in MITE while necessarily most of them, but not all, are in MATE. However, if we consider superpositions of energy eigenfunctions (i.e., typical wave functions ψ) in an energy shell, then for generic macroscopic systems, including those with MBL, most ψ are in both MATE and MITE. We explore here the properties of MATE and MITE and compare the two notions, thereby elaborating on ideas introduced in . image
In joint work with J. L. Lebowitz, C. Mastrodonato, and N. Zanghì [2, 3, 4], we considered an isolated, macroscopic quantum system. Let H be a micro‐canonical “energy shell,” i.e., a subspace of the system’s Hilbert space spanned by the (finitely) many energy eigenstates with energies between E and E+δE. The thermal equilibrium macro‐state at energy E corresponds to a subspace Heq of H such that dimHeq/dimH is close to 1. We say that a system with state vector ψ ε H is in thermal equilibrium if ψ is “close” to Heq. We argue that for “typical” Hamiltonians, all initial state vectors ψ0 evolve in such a way that ψt is in thermal equilibrium for most times t. This is closely related to von Neumann’s quantum ergodic theorem of 1929.
In joint work with J. L. Lebowitz, C. Mastrodonato, and N. Zanghì [2, 3, 4], we considered an isolated, macroscopic quantum system. Let H be a micro‐canonical “energy shell,” i.e., a subspace of the system’s Hilbert space spanned by the (finitely) many energy eigenstates with energies between E and E+δE. The thermal equilibrium macro‐state at energy E corresponds to a subspace Heq of H such that dimHeq/dimH is close to 1. We say that a system with state vector ψ ε H is in thermal equilibrium if ψ is “close” to Heq. We argue that for “typical” Hamiltonians, all initial state vectors ψ0 evolve in such a way that ψt is in thermal equilibrium for most times t. This is closely related to von Neumann’s quantum ergodic theorem of 1929.
We consider the notion of thermal equilibrium for an individual closed macroscopic quantum system in a pure state, i.e., described by a wave function. The macroscopic properties in thermal equilibrium of such a system, determined by its wave function, must be the same as those obtained from thermodynamics, e.g., spatial uniformity of temperature and chemical potential. When this is true we say that the system is in macroscopic thermal equilibrium (MATE). Such a system may, however, not be in microscopic thermal equilibrium (MITE). The latter requires that the reduced density matrices of small subsystems be close to those obtained from the microcanonical, equivalently the canonical, ensemble for the whole system. The distinction between MITE and MATE is particularly relevant for systems with many-body localization for which the energy eigenfuctions fail to be in MITE while necessarily most of them, but not all, are in MATE. We note, however, that for generic macroscopic systems, including those with MBL, most wave functions in an energy shell are in both MATE and MITE. For a classical macroscopic system, MATE holds for most phase points on the energy surface, but MITE fails to hold for any phase point.
Classical statistical mechanics/thermodynamics is sometimes portrayed as an approximate approach to describing the classical mechanical motion of very large numbers of particles. Equilibrium statistical mechanics/thermodynamics, however, is a special situation in which thermodynamic averages such as temperature, pressure etc do not change in time. We argue in this note that this is due to constraints imposed on such equilibrium scenarios namely time reversal reaction balance. It is this (approximate) constraint which yields the Maxwell-Boltzmann distribution which in turn defines average values of classical values e.g. pressure resulting from an average of bvv (b=constant) and temperature being related to average kinetic energy. Interestingly, average values such as average energy and pressure may yield a classical mechanical relationship for adiabatic processes, otherwise the more complicated dE=TdS - PdV applies to these averages. (To be more accurate one may use the constraints of microcanonical theory.) Quantum mechanics is also a statistical theory because a single particle with a fixed momentum is characterized by a physical wavelength region and a probability distribution exp(ipx). If interactions occur with potential regions a superposition of these distributions (i.e. a momentum superposition) occurs i.e. W(x)= Sum over p a(p)exp(ipx). This represents one constraint in quantum mechanics), but there is a second, namely that averages for a bound system match classical values. Thus, like classical statistical mechanics one may imagine a system characterized by a parameter say L (box length) which changes such that the particle stays in the same quantum state (i.e. an adiabatic change). Given that bound quantum mechanics is constrained to behave on average as a classical system it is not surprising that a dE=PdV which is essentially a Newton’s second law statement dE=Fdx and is not necessarily linked to a usual statistical system. If a quantum state has its parameter changed nonadiabatically it should be able to have it change into a superposition of new quantum states (new L) which is very different from the classical statistical mechanical scenario. Furthermore the ideal gas relationship PV=NRT and E=3/2NRT (3 degrees of freedom) or PV=(⅔)E matches a classical mechanical result because a particle with p may bounce from a wall yielding an impulse. In this note we try to examine some of these underlying constraints and argue that even dE=PdV for average E and P values (i.e. no entropy change) one must be aware of the specific constraints involved. In other words because dE=PdV for both adiabatic classical statistical mechanical systems and a quantum eigenstate, these do not necessarily represent the same statistical type of physics. We further argue that quantum mechanical bound states are constrained to have some average and rms values such as KE(x) and p rms behave as classical values and so these should not be taken to represent “intrinsic” quantum behaviour while average spatial density on the other hand does. (It is linked to the constraint of wavelength.)
We treat the problem of the approach to thermal equilibrium by only resorting to quantum dynamics of an isolated macroscopic system. Inspired by the two important works in 2009 and in 1929, we have noted that a condition we call "thermodynamic normality" for a macroscopic observable guarantees the approach to equilibrium (in the sense that a measurement of the observable at time t almost certainly yields a result close to the corresponding microcanonical average for a sufficiently long and typical t). A crucial point is that we make no assumptions on the initial state of the system, except that its energy is distributed close to a certain macroscopic value. We also present three (rather artificial) models in which the thermodynamic normality can be established, thus providing concrete examples in which the approach to equilibrium is rigorously justified. Note that this kind of results which hold for ANY initial state are never possible in classical systems. We are thus dealing with a mechanism which is peculiar to quantum systems. The present note is written in a self-contained (and hopefully readable) manner. It only requires basic knowledge in quantum physics and equilibrium statistical mechanics.