Different Environments in Quantum Statistical Mechanics: To $\beta$ or not to $(k_{\mathrm{B}} T)^{-1}$

Abstract

We piece together textbook material to re-derive the parameter $\beta$ entering reduced density operators from quantum statistical mechanics. By re-deriving $\beta$, we show that the content of $\beta$ depends on the particular application of statistical mechanics. We focus on two different applications, namely, electronic-structure theory (new) and thermodynamics (standard). Specifically, we show that $\beta$ becomes proportional to the inverse Fermi energy, when the electronic states of a system interact with the infinitely many valence electrons in a metal. On the other hand, when the environment is a heat bath, $\beta$ takes the well-known form of inverse temperature. To highlight the importance of using the correct form of $\beta$, we explore statistical descriptions of a potassium atom adsorbed on a gold surface, where the valence electrons of gold represent the environment of potassium. By treating $\beta$ as the inverse Fermi energy, we are able to qualitatively reproduce the fractional charging of potassium. In contrast, if we interpret $\beta$ as the inverse temperature, extremely high and unphysical temperatures are required to reproduce the same qualitative picture. Thereby, we illustrate the fallacy of not separating the mathematical framework of quantum statistical mechanics from its pervasive thermodynamic application.