The Structure of the First Coordination Shell in Liquid Water

Wernet, Philippe; Nordlund, Dennis; Bergmann, Uwe; Cavalleri, Matteo; Odelius, Michael; Ogasawara, Hirohito; Näslund, Lars-Åke; Hirsch, Tomas K.; Ojamäe, Lars; Glatzel, Pieter; Pettersson, Lars G. M.; Nilsson, Anders

doi:10.1126/science.1096205

Cited by 1,348 publications

(1,434 citation statements)

References 25 publications

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“…Coulomb perhaps with polarizability plus Lennard-Jones) seem to be very successful in reproducing many of the structural and thermodynamic properties of water 78,79 . However, the failure of classical molecular dynamics simulations to reproduce the controversial "chains and rings" structure of liquid water, inferred from recent X-ray absorption and X-ray Raman scattering experiments 2 , has generated questions about the reliability of existing water potentials 2,76,80 . This fact, combined with the predominantly CT character of the hydrogen bonding suggested by NBO, has led to proposals to incorporate CT effects into empirical water potentials 76 .…”

Section: Physical Nature Of Hydrogen Bonding In the Water Dimermentioning

confidence: 99%

“…The time behaviour described above implies that the instantaneous asymmetry can, in principle, be detected by X-ray spectroscopy, which has tem- poral resolution of several femtoseconds and is highly sensitive to perturbations in the electronic structure of molecules 2,156 . To identify possible relationships between the spectroscopic features and asymmetry, the XA spectrum of liquid water is calculated at the oxygen K-edge.…”

Section: Liquid Water a Structural And Dynamical Properties Of Lmentioning

confidence: 99%

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Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

Khaliullin

Kühne

2013

Phys. Chem. Chem. Phys.

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The application of newly developed first-principle modeling techniques to liquid water deepens our understanding of the microscopic origins of its unusual macroscopic properties and behaviour. Here, we review two novel ab initio computational methods: second-generation Car-Parrinello molecular dynamics and decomposition analysis based on absolutely localized molecular orbitals. We show that these two methods in combination not only enable ab initio molecular dynamics simulations on previously inaccessible time and length scales, but also provide unprecedented insights into the nature of hydrogen bonding between water molecules. We discuss recent applications of these methods to water clusters and bulk water. CONTENTS

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Section: Physical Nature Of Hydrogen Bonding In the Water Dimermentioning

confidence: 99%

Section: Liquid Water a Structural And Dynamical Properties Of Lmentioning

confidence: 99%

Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

Khaliullin

Kühne

2013

Phys. Chem. Chem. Phys.

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“…We considered absorption spectra of individual water molecules derived from two extrema for these simulations: large tilt angles close to or greater than 160°and smaller tilt angles around 120°or less. The effect of tilt angle on X-ray absorption spectral features has been previously considered in model systems of water-water interactions 39 and in ion-water 'dimers'. 18 In both cases, some shift of the spectral features toward higher energies occurred for larger tilt angle values.…”

Section: Comparisons Of Xas and Structure For Monovalent And Divalmentioning

confidence: 99%

Local Effects in the X-ray Absorption Spectrum of Salt Water

et al. 2010

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Both first-principles molecular dynamics and theoretical X-ray absorption spectroscopy have been used to investigate the aqueous solvation of cations in 0.5 M MgCl 2 , CaCl 2 , and NaCl solutions. We focus here on the species-specific effects that Mg 2+ , Ca 2+ , and Na + have on the X-ray absorption spectrum of the respective solutions. For the divalent cations, we find that the hydrogen-bonding characteristics of the more rigid magnesium first-shell water molecules differ from those in the more flexible solvation shell surrounding calcium. In particular, the first solvation shell water molecules of calcium are able to form acceptor hydrogen bonds, and this results in an enhancement of a post-edge peak near 540 eV. The absence of acceptor hydrogen bonds for magnesium first shell water molecules provides an explanation for the experimental and theoretical observation of a lack of enhancement at the post-main-edge peak. For the sodium monovalent cation we find that the broad tilt angle distribution results in a broadening of postedge features, despite populations in donorand-acceptor configurations consistent with calcium. We also present the reaveraged spectra of the MgCl 2 , CaCl 2 , and NaCl solutions and show that trends apparent with increasing concentration (0.5, 2.0, 4.0 M) are consistent with experiment. Finally, we examine more closely both the effect that cation coordination number has on the hydrogen-bonding network and the relative perturbation strength of the cations on lone pair oxygen orbitals.

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“…Following the publication of the article by Wernet et al in 2004, 2 this view has been challenged by a heterogeneous model of liquid water in which the thermal fluctuations are instead centered around two separate underlying structural motifs. This hypothesis was initially based on results from X-ray absorption spectroscopy (XAS) and X-ray Raman scattering (XRS) measurements, as these techniques are especially suitable for the determination of local molecular structure -the time-scale of a core-excitation is of the order of attoseconds, while the H-bond dynamics occur on a time-scale of hundreds of femtoseconds.…”

Section: Introductionmentioning

confidence: 99%

Requirements of first-principles calculations of X-ray absorption spectra of liquid water

Fransson

Zhovtobriukh

Coriani

et al. 2016

Phys. Chem. Chem. Phys.

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1 Abstract A computational benchmark study on X-ray absorption spectra of water has been performed by means of transition-potential density functional theory (TP-DFT), damped time-dependent density functional theory (TDDFT), and damped coupled cluster (CC) linear response theory. For liquid water, using TDDFT with a tailored CAM-B3LYP functional and a polarizable embedding, we find that an embedding with over 2000 water molecules is required to fully converge spectral features for individual molecules, but a substantially smaller embedding can be used within averaging schemes.TP-DFT and TDDFT calculations on 100 MD structures demonstrate that TDDFT produces a spectrum with spectral features in good agreement with experiment, while it is more difficult to fully resolve the spectral features in the TP-DFT spectrum. Similar trends were also observed for calculations of bulk ice. In order to further establish the performance of these methods, small water clusters have been considered also at the CC2 and CCSD levels of theory. Issues regarding the basis set requirements for spectrum simulations of liquid water and the determination of gas-phase ionization potentials are also discussed.2

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The Structure of the First Coordination Shell in Liquid Water

Cited by 1,348 publications

References 25 publications

Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

Local Effects in the X-ray Absorption Spectrum of Salt Water

Requirements of first-principles calculations of X-ray absorption spectra of liquid water

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