Hydrogen bonds in liquid water studied by photoelectron spectroscopy

Winter, Bernd; Aziz, Emad F.; Hergenhahn, U.; Faubel, Manfred; Hertel, I. V.

doi:10.1063/1.2710792

Cited by 163 publications

(197 citation statements)

References 33 publications

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“…[57][58][59] Core-level photoelectron spectroscopy of liquid water shows only one O1s peak as well, but in this case the O1s peak is broad enough to support two unresolved features within the separation between the two 1b 1 peaks in XES. 60 Here, we will discuss various hypotheses that can explain the current data. We are thereby revisiting an old discussion, 25 but with a focus on that the temperature dependence is somewhat unexpected.…”

Section: Discussionmentioning

confidence: 99%

X-ray emission spectroscopy of bulk liquid water in “no-man’s land”

Sellberg

McQueen

Laksmono

et al. 2015

The Journal of Chemical Physics

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The structure of bulk liquid water was recently probed by x-ray scattering below the temperature limit of homogeneous nucleation (T H ) of ∼232 K [J. A. Sellberg et al., Nature 510, 381-384 (2014)]. Here, we utilize a similar approach to study the structure of bulk liquid water below T H using oxygen K-edge x-ray emission spectroscopy (XES). Based on previous XES experiments [T. Tokushima et al., Chem. Phys. Lett. 460, 387-400 (2008)] at higher temperatures, we expected the ratio of the 1b 1 ′ and 1b 1 ′′ peaks associated with the lone-pair orbital in water to change strongly upon deep supercooling as the coordination of the hydrogen (H-) bonds becomes tetrahedral. In contrast, we observed only minor changes in the lone-pair spectral region, challenging an interpretation in terms of two interconverting species. A number of alternative hypotheses to explain the results are put forward and discussed. Although the spectra can be explained by various contributions from these hypotheses, we here emphasize the interpretation that the line shape of each component changes dramatically when approaching lower temperatures, where, in particular, the peak assigned to the proposed disordered component would become more symmetrical as vibrational interference becomes more important. C 2015 AIP Publishing LLC. [http://dx

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Section: Discussionmentioning

confidence: 99%

X-ray emission spectroscopy of bulk liquid water in “no-man’s land”

Sellberg

McQueen

Laksmono

et al. 2015

The Journal of Chemical Physics

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“…The dynamical structure of ambient water and the molecular picture of its important role in chemical and biological systems, often associated with a distinctive local struc-ture of hydrogen bonds [9,50] has been studied with powerful spectroscopic techniques in the past [51][52][53][54]. Nevertheless, the degree of understanding is often not sufficient.…”

Section: Dynamics In Extreme States Of Watermentioning

confidence: 99%

“…Only after Faubel et al developed the liquid beam technique in vacuum also volatile liquids like water could be investigated with photoelectron spectroscopy in vacuum [5][6][7][8]. Since then, the chemical shift in the static ESCA approach has also been a particularly powerful observable for probing electron densities and molecular orbital energies in different liquid molecular environments [9,10].…”

Section: Esca and Photoelectron Spectroscopy Near Liquid Interfaces Xmentioning

confidence: 99%

Ultrafast electronic spectroscopy for chemical analysis near liquid water interfaces: concepts and applications

et al. 2009

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Electron spectroscopy for chemical analysis (ESCA) being conceptually a photoelectron spectroscopy is established as a chemically specific probe mostly for surface analysis. Liquid phase ESCA for volatile liquids has become possible through the development of the liquid microjet technique in vacuum enabling the measurement of liquid interface photoelectron emission at the high vapor pressure of volatile liquids. Recently we have been able to add the dimension of time to the liquid interface ESCA technique employing high-harmonics soft X-ray and UV/near IR femtosecond pulses in combination with liquid water micro beams in vacuum. The concepts as well as technical details are outlined and several characteristic applications are high-

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“…In Figure 2a the photon energy is 600 eV, i.e., sufficient to cause direct core-ionization, being more than 60 eV above the O1s ionization threshold of liquid water. 40 The spectrum in (see below), this peak has no gas-phase analogue, 27 and is the unambiguous electronicstructure signature of 1h•1h final states, whose energies are lower than for the 2h states, thus leading to higher KE of the outgoing electron in the autoionization event. Our interpretation of the shoulder at 510 eV KE is further supported by our constrained DFT calculations on small water clusters presented below and in the Supplementary Information (SI), Figures S1 and S2.…”

Section: Core-level Ionization Induced Autoionization Spectra: H 2 O(mentioning

confidence: 99%

On the nature and origin of dicationic, charge-separated species formed in liquid water on X-ray irradiation

et al. 2013

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Identifying the initial products of the interaction of high-energy radiation with liquidwater is essential for understanding the yield and patterns of damage in aqueous condensed matter, including biological systems. Up until now several fast reactions induced by energetic particles in water could not be observed on their characteristic timescales, and hence some of the reaction intermediates involved, particularly those requiring nuclear motion, have not been considered in describing radiation chemistry.Here, through a combined experimental and theoretical study, we elucidate the ultrafast proton dynamics in the first few femtoseconds after X-ray core-level ionization of liquid water. We show through isotope analysis of the Auger-spectra that proton-transfer dynamics occurs on the same timescale as electron autoionization. Proton transfer leads to formation of a Zundel-type intermediate [HO*··H··OH 2 ] + , which further ionizes, forming a so-far unnoticed type of di-cationic, charge-separated species with high internal energy. We call the process proton-transfer mediated charge separation.The primary processes in water initiated by X-radiation are poorly understood despite their paramount importance in different fields. Understanding the energy and charge redistribution in water upon X-ray photon absorption is vital for a design of more efficient radio-oncology schemes, 1-2 for disentangling the physical basis of genotoxic effects on living tissues, [3][4][5] for minimizing the damage of biological samples during X-ray diffraction 2 experiments, 6 as well as for controlling the performance of nuclear reactors under operating conditions. 7 Current understanding of electron-initiated processes in aqueous systems, following energy deposition, and the subsequent radical chemistry have been recently reviewed. 8 An explicit consideration of radicals and molecular species formed via multiple ionization processes of water, involving for instance atomic oxygen and hydrogen peroxide, can be found in the radiolysis literature, e.g. in refs. 7,9 However, the knowledge of the ultrafast processes and mechanisms in water radiolysis remains to large extent unexplored.In the present work we focus on the processes following O1s core-level ionization of water. The highly excited species formed by the core ionization relaxes primarily via Augerelectron decay. As shown in Figure 1b, Auger decay of a water molecule involves refilling the water core-hole by one of the valence electrons, and the simultaneous emission of another valence electron, the Auger electron, from the same water molecule. The resulting highly reactive doubly ionized H 2 O 2+ (aq) molecule, with both vacancies (holes) located at the same site (denoted here as 2h state), then undergoes ultrafast Coulomb explosion, forming dominantly O + 2H + . [10][11] In recent years a set of novel non-local autoionization processes has been identified to play an important role in weakly bonded atomic and molecular systems. [12][13][14] One such relaxation process is Intermolecu...

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Hydrogen bonds in liquid water studied by photoelectron spectroscopy

Cited by 163 publications

References 33 publications

X-ray emission spectroscopy of bulk liquid water in “no-man’s land”

X-ray emission spectroscopy of bulk liquid water in “no-man’s land”

Ultrafast electronic spectroscopy for chemical analysis near liquid water interfaces: concepts and applications

On the nature and origin of dicationic, charge-separated species formed in liquid water on X-ray irradiation

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