Optical measurement of the picosecond fluid mechanics in simple liquids generated by vibrating nanoparticles: a review

Abstract

Standard continuum assumptions commonly used to describe the fluid mechanics of simple liquids have the potential to break down when considering flows at the nanometer scale. Two common assumptions for simple molecular liquids are that (1) they exhibit a Newtonian response, where the viscosity uniquely specifies the linear relationship between the stress and strain rate, and (2) the liquid moves in tandem with the solid at any solid–liquid interface, known as the no-slip condition. However, even simple molecular liquids can exhibit a non-Newtonian, viscoelastic response at the picosecond time scales that are characteristic of the motion of many nanoscale objects; this viscoelasticity arises because these time scales can be comparable to those of molecular relaxation in the liquid. In addition, even liquids that wet solid surfaces can exhibit nanometer-scale slip at those surfaces. It has recently become possible to interrogate the viscoelastic response of simple liquids and associated nanoscale slip using optical measurements of the mechanical vibrations of metal nanoparticles. Plasmon resonances in metal nanoparticles provide strong optical signals that can be accessed by several spectroscopies, most notably ultrafast transient-absorption spectroscopy. These spectroscopies have been used to measure the frequency and damping rate of acoustic oscillations in the nanoparticles, providing quantitative information about mechanical coupling and exchange of mechanical energy between the solid particle and its surrounding liquid. This information, in turn, has been used to elucidate the rheology of viscoelastic simple liquids at the nanoscale in terms of their constitutive relations, taking into account separate viscoelastic responses for both shear and compressible flows. The nanoparticle vibrations have also been used to provide quantitative measurements of slip lengths on the single-nanometer scale. Viscoelasticity has been shown to amplify nanoscale slip, illustrating the interplay between different aspects of the unconventional fluid dynamics of simple liquids at nanometer length scales and picosecond time scales.

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