The end of ice I.

The appearance of ice I in the smallest possible clusters and the nature of its phase coexistence with liquid water could not thus far be unraveled. The experimental and theoretical infrared spectroscopic and free-energy results of this work show the emergence of the characteristic hydrogen-bonding pattern of ice I in clusters containing only around 90 water molecules. The onset of crystallization is accompanied by an increase of surface oscillator intensity with decreasing surface-to-volume ratio, a spectral indicator of nanoscale crystallinity of water. In the size range from 90 to 150 water molecules, we observe mixtures of largely crystalline and purely amorphous clusters. Our analysis suggests that the liquid-ice I transition in clusters loses its sharp 1st-order character at the end of the crystalline-size regime and occurs over a range of temperatures through heterophasic oscillations in time, a process without analog in bulk water.

Temperature evolution in IR action spectroscopy experiments with sodium doped water clusters.

The combination of supersonic expansions with IR action spectroscopy techniques is the basis of many successful approaches to study cluster structure and dynamics. The effects of temperature and temperature evolution are important with regard to both the cluster synthesis and the cluster dynamics upon IR excitation. In the past the combination of the sodium doping technique with IR excitation enhanced near threshold photoionization has been successfully applied to study neutral, especially water clusters. In this work we follow an overall examination approach for inspecting the interplay of cluster temperature and cluster structure in the initial cooling process and in the IR excitation induced heating of the clusters. In molecular simulations, we study the temperature dependent photoionization spectra of the sodium doped clusters and the evaporative cooling process by water molecule ejection at the cluster surface. We present a comprehensive analysis that provides constraints for the temperature evolution from the nozzle to cluster detection in the mass spectrometer. We attribute the IR action effect to the strong temperature dependence of sodium solvation in the IR excited clusters and we discuss the effects of geometry changes during the IR multi-photon absorption process with regard to application prospects of the method.

Revealing isomerism in sodium-water clusters: Photoionization spectra of Na(H2O)n (n = 2-90).

Soft ionization of sodium tagged polar clusters is increasingly used as a powerful technique for sizing and characterization of small aerosols with possible application, e.g., in atmospheric chemistry or combustion science. Understanding the structure and photoionization of the sodium doped clusters is critical for such applications. In this work, we report on measurements of photoionization spectra for sodium doped water clusters containing 2-90 water molecules. While most of the previous studies focused on the ionization threshold of the Na(H2O)n clusters, we provide for the first time full photoionization spectra, including the high-energy region, which are used as reference for a comparison with theory. As reported in previous work, we have seen an initial drop of the appearance ionization energy with cluster size to values of about 3.2 eV for n<5. In the size range from n = 5 to n = 15, broad ion yield curves emerge; for larger clusters, a constant range between signal appearance (∼2.8 eV) and signal saturation (∼4.1 eV) has been observed. The measurements are interpreted with ab initio calculations and ab initio molecular dynamics simulations for selected cluster sizes (n≤ 15). The simulations revealed theory shortfalls when aiming at quantitative agreement but allowed us identifying structural motifs consistent with the observed ionization energy distributions. We found a decrease in the ionization energy with increasing coordination of the Na atom and increasing delocalization of the Na 3s electron cloud. The appearance ionization energy is determined by isomers with fully solvated sodium and a highly delocalized electron cloud, while both fully and incompletely solvated isomers with localized electron clouds can contribute to the high energy part of the photoionization spectrum. Simulations at elevated temperatures show an increased abundance of isomers with low ionization energies, an entropic effect enabling size selective infrared action spectroscopy, based on near threshold photoionization of Na(H2O)n clusters. In addition, simulations of the sodium pick-up process were carried out to study the gradual formation of the hydrated electron which is the basis of the sodium-tagging sizing.

Size-resolved infrared spectroscopic study of structural transitions in sodium-doped (H2O)n clusters containing 10-100 water molecules.

In water clusters containing 10-100 water molecules the structural transition takes place between "all surface" structures without internally solvated water molecules to amorphous water clusters with a three dimensionally structured interior. This structural evolution is explored with rigorous size selection by IR excitation modulated photoionization spectroscopy of sodium-doped (H2O)n clusters. The emergence of fully coordinated interior water molecules is observed by an increased relative absorption from 3200 to 3400 cm(-1) in agreement with theoretical predictions and earlier experimental studies. The analysis has also shown that the intermediate-sized water clusters (n = 40-65) do not smoothly link the structures in the largest and smallest analyzed size regions (n = 15-35 and n = 100-150) in line with previous reports suggesting the appearance of exceptionally stable water cluster isomers at n = 51, 53, 55, and 57. In the size range from n = 49 to n = 55 a reduced ion yield, a plateau in the total IR signal gain and signatures in the distribution of free OH stretch oscillator absorption have been observed. Recently reported putative global minima structures for n = 51 and n = 54 point to the presence of periplanar interior rings in odd-numbered clusters in this size range, which may affect cluster (surface) stability and the shape of the free OH stretch absorption peak. Potential links between pure and sodium-doped water cluster structures and the signatures of solvated electrons in photoelectron spectra of anionic water clusters are discussed.

Infrared detection of (H2O)20 isomers of exceptional stability: a drop-like and a face-sharing pentagonal prism cluster.

Water clusters with internally solvated water molecules are widespread models that mimic the local environment of the condensed phase. The appearance of stable (H2O)n cluster isomers having a fully coordinated interior molecule has been theoretically predicted to occur around the n = 20 size range. However, our current knowledge about the size regime in which those structures become energetically more stable has remained hypothetical from simulations in lieu of the absence of precisely size-resolved experimental measurements. Here we report size and isomer selective infrared (IR) spectra of (H2O)20 clusters tagged with a sodium atom by employing IR excitation modulated photoionization spectroscopy. The observed absorption patterns in the OH stretching region are consistent with the theoretically predicted spectra of two structurally distinct isomers of exceptional stability: a drop-like cluster with a fully coordinated (interior) water molecule and an edge-sharing pentagonal prism cluster in which all atoms are on the surface. The drop-like structure is the first experimentally detected water cluster exhibiting the local connectivity found in liquid water.