Resonant inelastic X-ray scattering of liquid water

Nilsson, Anders; Tokushima, Takashi; Horikawa, Yoko; Harada, Yoshihisa; Ljungberg, Mathias P.; Shin, Shik; Pettersson, Lars G. M.

doi:10.1016/j.elspec.2012.09.011

Cited by 45 publications

(68 citation statements)

References 118 publications

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“…Indeed, the computed XE spectrum of the water dimer does not exhibit two distinct peaks but rather an asymmetrical 1b 1 line shape that can also explain the isotope effect. 25,34,35 Furthermore, the difference in binding energy between 1b 1 and O1s in photoelectron spectroscopy is nearly identical for OH and water, 26 thus not giving an extra feature in the 1b 1 region and, in addition, we would expect to see a distinct feature at 523 eV characteristic of a well-defined OH species. 25 A dissociative mechanism involving OH and giving a sharp spectral feature in the lone-pair spectrum, but not at 523 eV, thus cannot account for the dependence of the two peaks on temperature, 28 polarization, 27 and excitation energy.…”

Section: Discussionmentioning

confidence: 99%

“…25,34,35 Furthermore, the difference in binding energy between 1b 1 and O1s in photoelectron spectroscopy is nearly identical for OH and water, 26 thus not giving an extra feature in the 1b 1 region and, in addition, we would expect to see a distinct feature at 523 eV characteristic of a well-defined OH species. 25 A dissociative mechanism involving OH and giving a sharp spectral feature in the lone-pair spectrum, but not at 523 eV, thus cannot account for the dependence of the two peaks on temperature, 28 polarization, 27 and excitation energy. 20,25,27,28 A second possibility is that the two peaks observed in XES reflect an additional and different bimodal distribution than that given by distorted and tetrahedral H-bonds which then could have temperature dependence different from that expected for HDL and LDL from molecular dynamics simulations.…”

Section: Discussionmentioning

confidence: 99%

“…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%

“…19,31,32 This has recently been extensively reviewed 25 and excluded based both on highlevel theoretical simulations of a model water dimer 34,35 and polarization-dependent measurements. 27 It was shown that, although the potential energy surface in the core-excited state has its minimum at the accepting oxygen, the proton becomes delocalized between the two water molecules and the resulting O-H stretch has to be described as a superposition of several excited vibrational states, giving rise to important interference effects when the appropriate Kramers-Heisenberg formalism is applied.…”

Section: Discussionmentioning

confidence: 99%

“…18 In particular, recent x-ray emission (XE) spectra show a split of the lone-pair (1b 1 ) peak in water 19,20 that has been interpreted as arising from structures with distorted H-bonds (1b 1 ′′ ) and from tetrahedrally H-bonded structures (1b 1 ′ ). 18,[20][21][22][23][24][25][26][27] As the liquid temperature is raised, intensity is transferred from the low-energy 1b 1 ′ peak to the high-energy 1b 1 ′′ peak, but no broadening or additional features are observed. 20,28 Also, selective excitations show a clear correlation between the two 1b 1 peaks and the various resonances in the x-ray absorption spectrum of water consistent with the hypothesis of two structural motifs.…”

Section: Introductionmentioning

confidence: 99%

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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%

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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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SoftX‐Ray Fluorescence Spectroscopy

Muramatsu

2018

Encyclopedia of Analytical Chemistry

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Soft X‐ray fluorescence (SXF) spectroscopy is X‐ray fluorescence (XRF) spectroscopy for low‐ and middle‐atomic‐number elements whose X‐ray absorption edges are in the soft X‐ray (SX) region. Electron beams have been used as excitation probes for ( nonresonant or normal ) SXF spectroscopy in laboratories. In addition, synchrotron radiation (SR) beams have been utilized as excitation probes, enabling selective excitation near the X‐ray absorption threshold. Selectively excited SXF involves soft X‐ray scattering, which can be regarded as a resonant soft X‐ray emission (SXE) spectroscopy. SXF and SXE spectroscopies provide element‐, orbital‐, and symmetry‐specific information. Thus, they are powerful tools for chemical analysis and materials characterization. In this article, the principles of SXF/SXE spectroscopies and instrumentation focused on gratings are described. Examples of nonresonant ( normal ) SXF and resonant SXE spectroscopies are shown, and details of the spectral profiles are explained. Resonant SXE spectroscopy of liquid water and operando observations of the electrode reactions are also demonstrated as advanced chemical analyses.

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A Two-State Picture of Water and the Funnel of Life

Pettersson

2019

Springer Proceedings in Physics

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Here I show that experimental and simulation data on liquid water using vibrational (infrared and Raman) and X-ray (absorption and emission) spectroscopies, as well as recent data from X-ray scattering, are fully consistent with a two-state picture of water. At ambient conditions there are fluctuations between a dominating high-density liquid (HDL) and a low-density form (LDL). These are related to the two forms of amorphous ice at very low temperature, highdensity amorphous (HDA) and low-density amorphous (LDA), which interconvert in a firstorder-like transition. This transition line is assumed to continue into the so-called "No-man's land" as a liquid-liquid transition and terminate in a critical point with very large fluctuations between the two liquid forms. These fluctuations extend in a funnel-like region up to ambient temperatures and pressures and give water its unusual properties which are fundamental to life.With this picture we find simple, intuitive explanations of the anomalous properties of water, such as the density maximum at 4 C, why ice floats, and why the compressibility and heat capacity grow as the liquid is cooled. We summarize by noting that in this picture, water is not a complicated liquid, but two normal liquids with a complicated relationship.

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Resonant inelastic X-ray scattering of liquid water

Cited by 45 publications

References 118 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”

SoftX‐Ray Fluorescence Spectroscopy

A Two-State Picture of Water and the Funnel of Life

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