High resolution X-ray emission spectroscopy of water and its assignment based on two structural motifs

Tokushima, Takashi; Harada, Yoshihisa; Horikawa, Yoko; Takahashi, Osamu; Senba, Yasunori; Ohashi, Haruhiko; Pettersson, Lars G. M.; Nilsson, Anders; Shin, Shik

doi:10.1016/j.elspec.2010.02.008

Cited by 110 publications

(166 citation statements)

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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%

“…45 The fluence dependence experiment was performed at BL07LSU at SPring-8, Japan. The liquid flow-through cell system used was basically the same as used at BL17SU, 26 whereas the XE spectrometer has higher total energy resolution 46 (E/∆E ∼ 5000) than the one at BL17SU due to its long optical path length as well as coma-free mode operation. 47 The incident photon flux was varied by tuning the front end slit placed at the upper stream of the monochromator, which only changes the fluence but affects neither the energy resolution nor the spot size at the sample position.…”

Section: Experimental Setup At Bl17su and Bl07lsu Spring-8mentioning

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: Experimental Setup At Bl17su and Bl07lsu Spring-8mentioning

confidence: 99%

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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“…XES where the emitted x-ray fluorescence is dispersed with an x-ray monochromator and the fluorescence intensity is detected as a function of the emitted x-ray photon energy, is a method that combines all of the required properties: It is a photon in photon out technique that can be readily applied to the investigation of liquids and solid-liquid interfaces and examples for soft x-ray XES/RIXS on liquid samples can be found in (69)(70)(71)(72)(73)(74)(75)(76)(77)(78)(79)(80). In addition and as illustrated in Figure 2, it can be used to retrieve information on the valence electronic structure that is very similar to the information from valence PES.…”

Section: Discussionmentioning

confidence: 99%

Electronic structure in real time: mapping valence electron rearrangements during chemical reactions

Wernet

2011

Phys. Chem. Chem. Phys.

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The interest in following the evolution of the valence electronic structure of atoms and molecules during chemical reactions on a femtosecond time scale is discussed. By explicitly mapping the occupied part of the electronic structure with femtosecond pump-probe schemes one essentially follows the electrons making the bonds while the bonds change. This holds the key to unprecedented insight into chemical bonding in short-lived intermediates and reveals the coupled motion of electrons and nuclei. Examples from the recent literature on small molecules and anionic clusters in the gas phase and on atoms and molecules on surfaces using lab-based femtosecond laser methods are used to demonstrate the case. They highlight how the evolution of the valence electronic structure can be probed with time-resolved photoelectron spectroscopy with ultraviolet (UV) probe photon energies of up to 6 eV. It is shown how new insight can be gained by extending the probing wavelength into the vacuumultraviolet (VUV) region to photon energies of 20 eV and more by accessing the whole occupied valence electronic structure with time-resolved VUV photoelectron spectroscopy.Finally, the importance of soft x-ray free-electron lasers with probe photon energies of several hundred eV and femtosecond pulses and in particular the key role of femtosecond timeresolved soft x-ray emission spectroscopy or resonant inelastic x-ray scattering for mapping the electronic structure during chemical reactions is discussed.2

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“…[63][64][65] Other measurement have also been invoked to support the two-structure model, e.g. small angle X-ray scattering, 43,45 and in the end it is important to formulate a theory which can account for the many different properties and measurements.…”

Section: Low-density Liquidmentioning

confidence: 99%

X-ray spectroscopies through damped linear response theory

Fransson¹

2016

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In order to reach a fundamental understanding of interactions between electromagnetic radiation and molecular materials, experimental measurements need to be supplemented with theoretical models and simulations. With the use of this combination, it is possible to characterize materials in terms of, e.g., chemical composition and molecular structure, as well as achieve time-resolution in studies of chemical reactions. This doctoral thesis focuses on the development and evaluation of theoretical methods with which, amongst others, X-ray absorption and X-ray emission spectroscopies can be interpreted and predicted. In X-ray absorption spectroscopy the photon energy is tuned such that core electrons are targeted and excited to either bound or continuum states, and X-ray emission spectroscopy measures the subsequent decay from such an excited state. These core excitations/de-excitations exhibit strong relaxation effects, making theoretical considerations of the processes particularly challenging. While the removal of a valence electron leaves the remaining electrons relatively unaffected, removing core electrons has a substantial effect on the other electrons due to the significant change in the screening of the nucleus. Additionally, the core-excited states are embedded in a manifold of valence-excited states that needs to be considered by some computationally feasible method. In this thesis, a damped formalism of linear response theory, which is a perturbative manner of considering the interactions of (weak) external or internal fields with molecular systems, has been utilized to investigate mainly the X-ray absorption spectra of small-to medium-sized molecular systems.Amongst the standard quantum chemical methods available, coupled cluster is perhaps the most accurate, with a well-defined, hierarchical manner of approaching the correct electronic wave function. Combined with response theory, it provides a reliable theoretical method in which relaxation effects are addressed by means of an accurate treatment of electron correlation. The first part of this thesis deals with the development and evaluation of such an approach, and it is shown that the relaxation effects can be addressed by the inclusion of double excitations in the coupled cluster manifold. However, these calculations are computationally very demanding, and in order to treat larger systems the performance of the coupled cluster approach has been compared to that of the less demanding method of timedensity dependent functional theory (TDDFT). Both methods have been used to v vi investigate the X-ray absorption spectrum of water, which has been extensively debated in the scientific community following a relatively recent hypothesis concerning the underlying structure of liquid water. Water exhibits a great number of anomalous properties that stand out from those of most compounds, and the importance of reaching a fundamental understanding of this substance cannot be overstated. It has been demonstrated that TDDFT yields excellent results for liq...

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High resolution X-ray emission spectroscopy of water and its assignment based on two structural motifs

Cited by 110 publications

References 57 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”

Electronic structure in real time: mapping valence electron rearrangements during chemical reactions

X-ray spectroscopies through damped linear response theory

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