Emergence of Debye scaling in the density of states of liquids under nanoconfinement

Abstract

In the realm of nanoscience, the dynamic behaviors of liquids at scales beyond the conventional structural relaxation time, $\tau$, unfold a fascinating blend of solid-like characteristics, including the propagation of collective shear waves and the emergence of elasticity. However, in classical bulk liquids, where $\tau$ is typically of the order of 1 ps or less, this solid-like behavior remains elusive in the low-frequency region of the density of states (DOS). Here, we provide evidence for the emergent solid-like nature of liquids at short distances through inelastic neutron scattering measurements of the low-frequency DOS in liquid water and glycerol confined within graphene oxide membranes. In particular, upon increasing the strength of confinement, we observe a transition from a liquid-like DOS (linear in the frequency $\omega$) to a solid-like behavior (Debye law, $\sim\omega^2$) in the range of $1$-$4$ meV. Molecular dynamics simulations confirm these findings and reveal additional solid-like features, including propagating collective shear waves and a reduction in the self-diffusion constant. Finally, we show that the onset of solid-like dynamics is pushed towards low frequency along with the slowing-down of the relaxation processes upon confinement. This nanoconfinement-induced transition, aligning with k-gap theory, underscores the potential of leveraging liquid nanoconfinement in advancing nanoscale science and technology, building more connections between fluid dynamics and materials engineering.