Physicochemical analysis of slip flow phenomena in liquids under nanoscale confinement

Eyring theory employs the statistical mechanical theory of absolute reaction rates to analyse the transport mechanisms in fluids. A physicochemical methodology combining molecular dynamics (MD) and Eyring theory of reaction rates is proposed for investigating the liquid slip on a solid wall in the nanoscale domain. The method involves the determination of activation energy required for the flow process directly from the MD trajectory information and then calculate the important transport properties of the confined fluid from the activation energy. In order to demonstrate the universal applicability of the proposed methodology in nanofluidics, the slip flow behavior of argon, water and ionic liquid confined in various nanostructures has been investigated. The slip length is found to be size dependent in all the cases. The novelty of this method is that the variations in slip length are explained on the basis of molecular interactions and the subsequent changes in the activation energy.