(Invited) Quasi Phase Transition in a Single File of Water Molecules Encapsulated inside (6,5) Carbon Nanotubes

Abstract

The confinement of water molecules in one-dimensional channels leads to fascinating new properties which are of critical importance for many processes in biology, geology, catalysis and nanofluidics. Single-walled carbon nanotubes (SWCNTs) are one of the most promising model systems to investigate molecules under confinement. They combined atomically-precise diameters that deliver the necessary level of confinement with a weak interaction of the water molecules with their smooth inner walls. Despite significant efforts, theoretical predictions of the behavior and peculiar properties of a single-file chain of water water molecules (e.g. interesting for ultrafast proton transport) have proven to be very hard to validate experimentally. In this work, we present temperature-dependent (4.2K up to room temperature) photoluminescence (PL) spectra of water-filled and empty chirality-sorted (6,5) SWCNTs. Superimposed on a linear temperature-depenent PL spectral shift of the empty tubes, an additional stepwise PL shift of the water-filled SWCNTs is observed at around 150K. With the empty SWCNTs serving as the ideal reference system, we can assign this observation to temperature-induced changes occuring within the single file molecular chain. Supported by new Molecular Dynamics simulations, we obtain the first experimental evidence of a quasi phase transition of the orientation of the molecular dipoles within such a one-dimensional single file chain of water molecules.