<p>Gas transport through nanochannels is critical to applications ranging from gas separation to shale gas extraction. Accurately predicting flow rates under non-adsorbing or weak-physisorption conditions requires the generalized Knudsen theory, which accounts for the full spectrum of gas-wall scattering mechanisms. However, its broad validation across diverse gases and surfaces remains incomplete, largely because the key parameter quantifying scattering, the diffuse reflection fraction (<i>f</i>) or tangential momentum accommodation coefficient (TMAC), is notoriously difficult to determine. Here, we employ molecular dynamics (MD) simulations to develop a robust approach for calculating <i>f</i>. Using this method, we systematically validate the generalized Knudsen theory for a wide range of gases, including all noble gases and common polyatomic species (H<sub>2</sub>, O<sub>2</sub>, H<sub>2</sub>O, CO<sub>2</sub> and CH<sub>4</sub>). Our results show that <i>f</i> or TMAC is predominantly a surface property: it clusters around 0.1 for graphene and 0.8 for SiO<sub>2</sub>, with only weak dependence on the gas species. By incorporating these <i>f</i> values, the theory achieves remarkable accuracy in predicting flow rates, as confirmed by direct MD simulations across all tested gas-channel combinations. This work establishes a general and predictive framework for gas transport in nanochannels, paving the way for the rational design of nanofluidic devices and advanced separation membranes.</p>

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Validation of the generalized Knudsen theory for diverse gas flow in nanochannels

  • HaoKe Peng,
  • HengAn Wu,
  • FengChao Wang

摘要

Gas transport through nanochannels is critical to applications ranging from gas separation to shale gas extraction. Accurately predicting flow rates under non-adsorbing or weak-physisorption conditions requires the generalized Knudsen theory, which accounts for the full spectrum of gas-wall scattering mechanisms. However, its broad validation across diverse gases and surfaces remains incomplete, largely because the key parameter quantifying scattering, the diffuse reflection fraction (f) or tangential momentum accommodation coefficient (TMAC), is notoriously difficult to determine. Here, we employ molecular dynamics (MD) simulations to develop a robust approach for calculating f. Using this method, we systematically validate the generalized Knudsen theory for a wide range of gases, including all noble gases and common polyatomic species (H2, O2, H2O, CO2 and CH4). Our results show that f or TMAC is predominantly a surface property: it clusters around 0.1 for graphene and 0.8 for SiO2, with only weak dependence on the gas species. By incorporating these f values, the theory achieves remarkable accuracy in predicting flow rates, as confirmed by direct MD simulations across all tested gas-channel combinations. This work establishes a general and predictive framework for gas transport in nanochannels, paving the way for the rational design of nanofluidic devices and advanced separation membranes.