Spectroscopic snapshot for neutral water nonamer (HO): Adding a HO onto a hydrogen bond-unbroken edge of (HO).

Structural characterization of neutral water clusters is crucial to understanding the structures and properties of water, but it has been proven to be a challenging experimental target due to the difficulty in size selection. Here, we report the size-specific infrared spectra of confinement-free neutral water nonamer (HO) based on threshold photoionization, using a tunable vacuum ultraviolet free-electron laser. Distinct OH stretch vibrational fundamentals in the 3200-3350 cm region are observed, providing unique spectral signatures for the formation of an unprecedented (HO) structure evolved by adding a ninth water molecule onto a hydrogen bond-unbroken edge of the (HO) octamer with D symmetry. This nonamer structure coexists with the five previously identified structures that can be viewed as derived by inserting a ninth water molecule into a hydrogen bond-broken edge of the D/S octamer. These findings provide key microscopic information for systematic understanding of the formation and growth mechanism of dynamical hydrogen-bonding networks that are responsible for the structure and properties of condensed-phase water.