This chapter has two goals. The first is to develop the quantum version of multiplicity. That will show us how entropy is expressed in quantum theory. The second goal is to develop a general quantitative definition of temperature. Entropy plays a key role in that definition.

The density of states

When a physical system has reached thermal equilibrium, its macroscopic properties do not change with time. In quantum theory, the energy eigenstates of an isolated system provide predictions and estimates that are constant in time; therefore such states are appropriate for a quantum description of thermal equilibrium.

To be sure, the information at hand will not enable us to select a single state as uniquely the correct state to use. We will be driven to consider many states and to form sums over them. This section develops a mathematical technique for working with such sums.

When the system is both isolated and of finite size (as we shall specify here), the energy eigenstates form a discrete set, whose members we can arrange and label in order of increasing energy. (If any two distinct states happen to have the same energy, we just assign them consecutive labels.) Typically, the states will be densely spaced in energy, and so a sum over a range of states can often be approximated adequately by an integral with respect to energy, provided that we have constructed an appropriate density of states: a function that specifies the number of energy eigenstates per unit energy interval.