Photoelectron spectroscopy of hydrated electrons

Shreve, Alexander T.; Yen, Terry A.; Neumark, Daniel M.

doi:10.1016/j.cplett.2010.05.059

Cited by 130 publications

(195 citation statements)

References 40 publications

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“…In line with previous measurements [23][24][25] it was found that charge carriers were needed to measure the photoelectron spectrum of a water sample. The high resistivity (18 M ) of the high performance liquid chromatography (HPLC) grade water used produced a large charging of the sample by the motion over the polyether ether ketone (PEEK) liquid jet tubing and fused silica nozzle.…”

Section: Results and Analysissupporting

confidence: 70%

A simple electron time-of-flight spectrometer for ultrafast vacuum ultraviolet photoelectron spectroscopy of liquid solutions

Arrell

Ojeda

Sabbar

et al. 2014

Review of Scientific Instruments

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Articles you may be interested inWe present a simple electron time of flight spectrometer for time resolved photoelectron spectroscopy of liquid samples using a vacuum ultraviolet (VUV) source produced by high-harmonic generation. The field free spectrometer coupled with the time-preserving monochromator for the VUV at the Artemis facility of the Rutherford Appleton Laboratory achieves an energy resolution of 0.65 eV at 40 eV with a sub 100 fs temporal resolution. A key feature of the design is a differentially pumped drift tube allowing a microliquid jet to be aligned and started at ambient atmosphere while preserving a pressure of 10 −1 mbar at the micro channel plate detector. The pumping requirements for photoelectron (PE) spectroscopy in vacuum are presented, while the instrument performance is demonstrated with PE spectra of salt solutions in water. The capability of the instrument for time resolved measurements is demonstrated by observing the ultrafast (50 fs) vibrational excitation of water leading to temporary proton transfer.

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Section: Results and Analysissupporting

confidence: 70%

A simple electron time-of-flight spectrometer for ultrafast vacuum ultraviolet photoelectron spectroscopy of liquid solutions

Arrell

Ojeda

Sabbar

et al. 2014

Review of Scientific Instruments

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“…In an attempt to probe interfacial CTTS dynamics of iodide, time-resolved photoelectron spectroscopy coupled with the liquid microject technique has recently been used. 6,[9][10][11][12][13] Results from such experiments showed that the observable dynamics are very similar to those seen in the bulk.…”

mentioning

confidence: 69%

“…A particularly useful means of initiating CTTS reactions is photoexcitation to CTTS absorption bands of certain aqueous anions. The most studied of these has been the CTTS of iodide [2][3][4][5][6][7][8][9][10][11][12][13] and a schematic of the solvation dynamics are shown in Figure 1. However, these studies have focussed on the bulk dynamics, while arguably, electron transfer reactions are of most interest at interfaces, be it on an aerosol particle, on an interstellar dust-grain, or at a water/biomolecule interface.…”

mentioning

confidence: 99%

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

Nowakowski

Woods

Verlet

2016

J. Phys. Chem. Lett.

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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%

“…(14,17) However, this issue can be rather subtle since water clusters prepared by supersonic jet expansion are not liquid but rather amorphous solids. As data on electron binding in liquid water have recently become directly accessible experimentally, (17)(18)(19)(20) applicability of cluster to bulk extrapolations has been vividly discussed recently (14,15,17,21,22) and will be also one of the subjects of this paper.…”

Section: Introductionmentioning

confidence: 96%

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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Photoelectron spectroscopy of hydrated electrons

Cited by 130 publications

References 40 publications

A simple electron time-of-flight spectrometer for ultrafast vacuum ultraviolet photoelectron spectroscopy of liquid solutions

A simple electron time-of-flight spectrometer for ultrafast vacuum ultraviolet photoelectron spectroscopy of liquid solutions

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

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

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