Impurity level in a crystal

A spatially localized electronic level produced by a defect or foreign atom in a crystalline potential. Such levels can lie in a host band gap, where no extended host state has the same energy, while impurity resonances can also occur inside an energy band. Dilute localized levels are nearly independent; increasing overlap can broaden them into an impurity band. The location and existence of a bound level depend on the impurity potential.

A localized orbital with two electron spin states has energies $E_0=0$, $E_1=ϵ$ and $E_2=2ϵ+U$. Its zero-temperature equilibrium occupation minimizes ${\mathcal{E}}_N=E_N-\mu N$, where $\mu$ is the chemical potential. For repulsion $U>0$, the occupation is successively $0,1,2$ as $\mu$ crosses $ϵ$ and $ϵ+U$. For attraction $U<0$, the singly occupied state is never the minimum: the occupation jumps from $0$ to $2$ at $\mu =ϵ+U/2$. Exactly at a crossing the ground-state occupation is not unique.

At positive temperature, its grand canonical partition function is $\Xi =1+2e^{-\beta (ϵ-\mu )}+e^{-\beta (2ϵ+U-2\mu )}$, where $\beta =1/(k_{B}T)$. The expected value of the occupation follows by differentiating: $⟨N⟩=k_{B}T{\partial }_{\mu }\ln \Xi$. The factor two counts the two singly occupied microstates, not an additional pair state.