Observation of Large Water-Cluster Anions with Surface-Bound Excess Electrons

Verlet, Jan R. R.; Bragg, Arthur E.; Kammrath, A.; Cheshnovsky, Ori; Neumark, Daniel M.

doi:10.1126/science.1106719

Cited by 383 publications

(577 citation statements)

References 27 publications

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“…Namely, the "cushion-like" structures occurring in cryogenic clusters have small values of VDE and are always located at the exterior of the cluster. (14,15,21,22) However, the situation concerning the more strongly bound structures, which appear both in cryogenic solids (14,15) and in warmer aqueous systems (17)(18)(19)(20) is more complicated.…”

Section: Structural Aspects Of Hydrated Electronsmentioning

confidence: 99%

“…This indicates that strongly and weakly bound excess electrons can coexist in ensembles of cryogenic clusters depending on their way of formation, as observed in the experiment. (14,15) The correlation between radius of gyration and VDE for the same data sets and using the same color coding as in Figure 4 is presented in Figure 5. The first thing to note is the very good overlap between the equilibrium points and data from localization trajectories at 300 K. The only part that is missing from the equilibrium data corresponds to the strongly delocalized and loosely bound structures from the onsets of the localization trajectories.…”

Section: Dynamical Aspects Of Hydrated Electronsmentioning

confidence: 99%

“…(12)(13)(14)(15) Already a water dimer is capable of binding an excess electron, (12) however, its character is very different from the bulk hydrated species. In small systems, these are weakly bound and very diffuse dipole-bound electrons, which reside at the exterior of the water cluster.…”

Section: Introductionmentioning

confidence: 99%

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Structure, Dynamics, and Reactivity of Hydrated Electrons by Ab Initio Molecular Dynamics

et al. 2011

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Understanding the properties of hydrated electrons, which were first observed using pulse radiolysis of water in 1962, is crucial because they are key species in many radiation chemistry processes. Although time-resolved spectroscopic studies and molecular simulations have shown that an electron in water (prepared, for example, by water photoionization) relaxes quickly to a localized, cavity-like structure similar to 2.5 angstrom in radius, this picture has recently been questioned. In another experimental approach, negatively charged water clusters of increasing size were studied with photoelectron and IR spectroscopies. Although small clusters can bind an excess electron, their character is very different from bulk hydrated species. As data on electron binding in liquid water have become directly accessible experimentally, the cluster-to-bulk extrapolations have become a topic of lively debate. Quantum electronic structure calculations addressing experimental measurables have, until recently, been largely limited to small clusters; extended systems were approached mainly with pseudopotential calculations combining a classical description of water with a quantum mechanical treatment of the excess electron. In this Account, we discuss our investigations of electrons solvated in water by means of ab initio molecular dynamics simulations. This approach, applied to a model system of a negatively charged cluster of 32 water molecules, allows us to characterize structural, dynamical, and reactive aspects of the hydrated electron using all of the system's valence electrons. We show that under ambient conditions, the electron localizes into a cavity close to the surface of the liquid cluster. This cavity is, however, more flexible and accessible to water molecules than an analogous area around negatively charged ions. The dynamical process of electron attachment to a neutral water cluster is strongly temperature dependent. Under ambient conditions, the electron relaxes in the liquid cluster and becomes indistinguishable from an equilibrated, solvated electron on a picosecond time scale. In contrast, for solid, cryogenic systems, the electron only partially localizes outside of the cluster, being trapped in a metastable, weakly bound "cushion-like" state. Strongly bound states under cryogenic conditions could only be prepared by cooling equilibrated, liquid, negatively charged clusters. These calculations allow us to rationalize how different isomers of electrons in cryogenic clusters can be observed experimentally. Our results also bring into question the direct extrapolation of properties of cryogenic, negatively charged water clusters to those of electrons in the bulk liquid. Ab initio molecular dynamics represents a unique computational tool for investigating the reactivity of the solvated electron in water. As a prototype, the electron proton reaction was followed in the 32-water cluster. In accord with experiment, the molecular mechanism is a proton transfer process that is not diffusion limited, but rat...

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Section: Structural Aspects Of Hydrated Electronsmentioning

confidence: 99%

Section: Dynamical Aspects Of Hydrated Electronsmentioning

confidence: 99%

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Structure, Dynamics, and Reactivity of Hydrated Electrons by Ab Initio Molecular Dynamics

et al. 2011

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“…Whether surface electron hydration dynamics are distinct from the bulk has been very topical since the observation of surface binding of hydrated electrons in water clusters [33][34][35] and thin ice films on metal surfaces 36,37 or metal oxide surfaces. 38 These surface-bound states are distinct from bulk e -(aq) because most of the electron's distribution is in the vapour phase.…”

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Charge Transfer to Solvent Dynamics at the Ambient Water/Air Interface

Nowakowski

Woods

Verlet

2016

J. Phys. Chem. Lett.

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“…DOI: 10.1103/PhysRevLett.112.157802 PACS numbers: 61.20.Ja, 64.60.Q−, 64.70.F− Water is presumably the most used and the most studied substance among all the chemicals known to mankind. In particular, scientists have been attracted to the diverse structures of water clusters, liquid, and ice resulting from different orientations of hydrogen bonds and the associated phenomena [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. However, the liquid-vapor transition of water has been a subject of less intense investigation [15,16] because of difficulties in both experiment and computation due to the complicated metastable states separating the liquid and vapor phases.…”

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Limit of Metastability for Liquid and Vapor Phases of Water

et al. 2014

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We report the limits of superheating of water and supercooling of vapor from Monte Carlo simulations using microscopic models with configurational enthalpy as the order parameter. The superheating limit is well reproduced. The vapor is predicted to undergo spinodal decomposition at a temperature of T vap sp ¼ 46 AE 10°C (0°C ≪ T vap sp ≪ 100°C) under 1 atm. The water-water network begins to form at the supercooling limit of the vapor. Three-dimensional water-water and cavity-cavity unbroken networks are interwoven at critically superheated liquid water; if either network breaks, the metastable state changes to liquid or vapor. DOI: 10.1103/PhysRevLett.112.157802 PACS numbers: 61.20.Ja, 64.60.Q−, 64.70.F− Water is presumably the most used and the most studied substance among all the chemicals known to mankind. In particular, scientists have been attracted to the diverse structures of water clusters, liquid, and ice resulting from different orientations of hydrogen bonds and the associated phenomena [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. However, the liquid-vapor transition of water has been a subject of less intense investigation [15,16] because of difficulties in both experiment and computation due to the complicated metastable states separating the liquid and vapor phases. Given that everyday life experiences water evaporation and dew drops, it is ironic that these physical or chemical phenomena are not adequately understood. Simply, we are familiar with the generally learned fact that water boils at 100°C or 373 K at 1 atm. However, water can be superheated up to 603 K at 1 atm, and water vapor can be supercooled considerably below the boiling point [17][18][19][20][21] though the limit of supercooling is not known yet. This is due to unfavorable energetics at the formation of the liquid-vapor interface, which allow for the temporary existence of metastable states. According to the classical nucleation theory, the metastable states can be kept stable until stochastic fluctuations create the so-called critical cluster, which then grows spontaneously to make a new phase [22].However, these metastable states cease to exist when the liquid or vapor is brought to its stability limit, or spinodal. In this case, where the mother phase completely loses its thermodynamic stability, the phase transition takes place via spinodal decomposition [23]. It differs from classical nucleation in which the phase transition takes place at localized regions of space. Instead, the phase transition is considered to proceed by merging small embryos of daughter phase distributed uniformly over the space [24]. The lifetime of systems near the stability limit is too short to allow for accurate experimental determination of the spinodal. Hence, predicting the stability limit from a microscopic model of matter is of immense importance, given that there are a plethora of phenomena depending on the metastability throughout biology, meteorology, and industry [22].In this Letter, based on targeted sampling of metastable and unsta...

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Observation of Large Water-Cluster Anions with Surface-Bound Excess Electrons

Abstract: Anionic water clusters have long been studied to infer properties of the bulk hydrated electron. We used photoelectron imaging to characterize a class of (H2O)n- and (D2O)n- cluster anions (n Show more

Cited by 383 publications

References 27 publications

Structure, Dynamics, and Reactivity of Hydrated Electrons by Ab Initio Molecular Dynamics

Structure, Dynamics, and Reactivity of Hydrated Electrons by Ab Initio Molecular Dynamics

Charge Transfer to Solvent Dynamics at the Ambient Water/Air Interface

Limit of Metastability for Liquid and Vapor Phases of Water

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