Thermal occupation of a quantum well ($p_1/p_0=e^{-(E_1-E_0)/(k_{B}T)}$)

For one nondegenerate thermalized particle, excited-state occupation relative to the ground state is set by the excitation gap, not by the absolute energy origin. In an infinite square well of width $L$, the first gap is $3{\pi }^2{\hslash }^2/(2m{L}^2)$. Predominant ground-state occupation requires this gap to be much larger than $k_{B}T$; an explicit tolerated occupation gives a quantitative temperature criterion. State quantum degeneracy adds its statistical weight.