This paper evaluates the suitability of a newly developed hybrid “Langmuir–Maxwell” and “Langmuir–Smoluchowski” slip/jump boundary conditions in the Navier–Stokes–Fourier equations for nano-/micro-backward-facing step geometry flow which experiences separation and reattachment. Additionally, this paper investigates the effect of different parameters such as step pressure ratio, inflow temperature, and wall temperature on the separation zone in the nano-/micro-step geometry. We chose nitrogen as the working gas and use two direct simulation Monte Carlo (DSMC) solvers to assess the accuracy of the computational fluid dynamics (CFD) solutions. DSMC results showed that the increase of the inlet temperatures extends the length of the separation ...