The Maxwell-Smoluchowski (MS) theory of gas diffusion is revisited here in the context of gas transport in straight channels in the Knudsen regime of large mean free path. This classical theory is based on a phenomenological model of gas-surface interaction that posits that a fraction ϑ of molecular collisions with the channel surface consists of diffuse collisions, i.e., the direction of post-collision velocities is distributed according to the Knudsen Cosine Law, and a fraction 1 − ϑ undergoes specular reflection. From this assumption one obtains the value D = 2 − ϑ ϑ D K for the self-diffusivity constant, where D K is a reference value corresponding to ϑ = 1. In this paper we show that ϑ can be expressed in terms of micro- and macro-geometric parameters for a model consisting of hard spheres colliding elastically against a rigid surface with prescribed microgeometry. Our refinement of the MS theory is based on the observation that the classical surface scattering operator associated to the microgeometry has a canonical velocity space diffusion approximation by a generalized Legendre differential operator whose spectral theory is known explicitly. More specifically, starting from an explicit description of the effective channel surface microgeometry—a concept which incorporates both the actual surface microgeometry and the molecular radius—and using this operator approximation, we show that ϑ can be resolved into easily obtained geometric parameters, ϑ = λ h / C , having the following interpretation: C is a macroscopic parameter determined by the shape of the channel cross-section; h is a parameter that precisely captures the degree of roughness of the effective microgeometry, and λ is a parameter that characterizes the overall curvature of the surface microgeometry independent of h. Thus ϑ is resolved as the quotient of microscopic (λh) over macroscopic (C) signature parameters of the channel geometry. The identity ϑ = λ h / C holds up to higher order terms in the roughness parameter h , so our main result better applies to well polished, or low roughness, surfaces. • The Maxwell-Smoluchowski theory of gas diffusion is revisited in the context of gas transport in straight channels in the Knudsen regime of large mean free path, in the special case of channel surface having low roughness. • A factorization of the phenomenological tangential momentum accommodation coefficient introduced in the Maxwell-Smoluchowski model is derived in terms of micro- and macro-geometric parameters based on a detailed analysis of the surface scattering of gas molecules under the assumption of low roughness. • A new concept of roughness is proposed which enters into the description of self-diffusivity in a more direct way than standard definitions, and these different notions of roughness are compared. • Utilizing a very simple model of micro-geometry, the new analysis obtains estimates for self-diffusivity of gas transport in carbon nanotubes in line with the very high values observed experimentally. [ABSTRACT FROM AUTHOR]