Page:Elementary Principles in Statistical Mechanics (1902).djvu/167

Rh Let us next consider whether an ensemble of isolated systems has any tendency in the course of time toward a state of statistical equilibrium.

There are certain functions of phase which are constant in time. The distribution of the ensemble with respect to the values of these functions is necessarily invariable, that is, the number of systems within any limits which can be specified in terms of these functions cannot vary in the course of time. The distribution in phase which without violating this condition gives the least value of the average index of probability of phase ($$\overline\eta$$) is unique, and is that in which the in various ways describe an ensemble in statistical equilibrium, while the same language applied to the critical value of the energy would fail to do so. Thus, if we should say that the ensemble is so distributed that the probability that a system is in any given part of the circle is proportioned to the time which a single system spends in that part, motion in either direction being equally probable, we should perfectly define a distribution in statistical equilibrium for any value of the energy except the critical value mentioned above, but for this value of the energy all the probabilities in question would vanish unless the highest point is included in the part of the circle considered, in which case the probability is unity, or forms one of its limits, in which case the probability is indeterminate. Compare the foot-note on page 118.

A still more simple example is afforded by the uniform motion of a material point in a straight line. Here the impossibility of statistical equilibrium is not limited to any particular energy, and the canonical distribution as well as the microcanonical is impossible.

These examples are mentioned here in order to show the necessity of caution in the application of the above principle, with respect to the question whether we have to do with a true case of statistical equilibrium.

Another point in respect to which caution must be exercised is that the part of an ensemble of which the theorem of the return of systems is asserted should be entirely defined by limits within which it is contained, and not by any such condition as that a certain function of phase shall have a given value. This is necessary in order that the part of the ensemble which is considered should be any assignable fraction of the whole. Thus, if we have a canonical ensemble consisting of material points in vertical circles, the theorem of the return of systems may be applied to a part of the ensemble defined as contained in a given part of the circle. But it may not be applied in all cases to a part of the ensemble defined as contained in a given part of the circle and having a given energy. It would, in fact, express the exact opposite of the truth when the given energy is the critical value mentioned above.