Abstract
It is shown, using Guggenheim's pressure ensemble that partial Gibbs free energies are the quantities determining equilibrium occupations of electronic levels and hence are the quantities that enter detailed balance relationships. It is also shown that the energy of an optical no-phonon transition between band states equals the corresponding free energy change. This is also true for transitions involving localized impurity states provided: 1. (a) the effects of electronic degeneracy are excluded from the free energy definition, and 2. (b) the localized state does not couple to a local phonon mode.
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