Growth and collapse of structural patterns in the hydrogen bond network in liquid water

Shiratani, Eli; Sasai, Masaki

doi:10.1063/1.471475

Cited by 161 publications

(169 citation statements)

References 30 publications

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“…Using the local structure index (LSI) (7,51) to identify high (I > 0.03) and low (I < 0.03) structured local coordinations results in an amount of high-LSI molecules of ∼50% at ambient conditions and a rapid decrease of this number with increasing p, T. However, a spatial statistical analysis of these subpopulations also shows no spatial correlations beyond r ) 5 Å even for the high-LSI molecules (SI Text), which indicates that molecules with different local environments are present at all simulated temperatures and pressures but are not spatially correlated beyond their characteristic distances (i.e., the second coordination shell). This is in line with the findings of English et al (4).…”

Section: Resultsmentioning

confidence: 99%

Microscopic structure of water at elevated pressures and temperatures

Sahle

Sternemann

Schmidt

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

135

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We report on the microscopic structure of water at sub-and supercritical conditions studied using X-ray Raman spectroscopy, ab initio molecular dynamics simulations, and density functional theory. Systematic changes in the X-ray Raman spectra with increasing pressure and temperature are observed. Throughout the studied thermodynamic range, the experimental spectra can be interpreted with a structural model obtained from the molecular dynamics simulations. A spatial statistical analysis using Ripley's K-function shows that this model is homogeneous on the nanometer length scale. According to the simulations, distortions of the hydrogenbond network increase dramatically when temperature and pressure increase to the supercritical regime. In particular, the average number of hydrogen bonds per molecule decreases to ≈0.6 at 600°C and p = 134 MPa.supercritical water | water structure | X-ray scattering | X-ray scattering spectroscopy

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Section: Resultsmentioning

confidence: 99%

Microscopic structure of water at elevated pressures and temperatures

Sahle

Sternemann

Schmidt

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

135

View full text Add to dashboard Cite

show abstract

“…To quantify the degree of inhomogeneity in the local molecular environments of liquid water, we have utilized an order parameter introduced by Shiratani and Sasai 31,32 , which associates a local structure index (LSI) to the individual water molecules comprising the liquid. In essence, the LSI order parameter is the mean-squareddeviation among the radial distances corresponding to the set of molecules that surround a given water molecule.…”

Section: B Local Structure Index (Lsi)mentioning

confidence: 99%

“…In this regard, recent studies have shown that the local structure index (LSI) 31,32 is a very insightful order parameter that can be employed to characterize the LDL and HDL molecular environments 23 . For instance, the distribution of the LSI order parameter was found to be bimodal in the corresponding inherent potential energy surface (IPES) of both supercooled and ambient liquid water [33][34][35] .…”

Section: Introductionmentioning

confidence: 99%

Local structure analysis in ab initio liquid water

et al. 2015

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Within the framework of density functional theory, the inclusion of exact exchange and non-local van der Waals/dispersion (vdW) interactions is crucial for predicting a microscopic structure of ambient liquid water that quantitatively agrees with experiment. In this work, we have used the local structure index (LSI) order parameter to analyze the local structure in such highly accurate ab initio liquid water. At ambient conditions, the LSI probability distribution, P(I), was unimodal with most water molecules characterized by more disordered high-density-like local environments. With thermal excitations removed, the resultant bimodal P(I) in the inherent potential energy surface (IPES) exhibited a 3:1 ratio between high-and low-density-like molecules, with the latter forming small connected clusters amid the predominant population. By considering the spatial correlations and hydrogen bond network topologies among water molecules with the same LSI identities, we demonstrate that the signatures of the experimentally observed low-(LDA) and highdensity (HDA) amorphous phases of ice are present in the IPES of ambient liquid water. Analysis of the LSI autocorrelation function uncovered a persistence time of ∼ 4 ps-a finding consistent with the fact that natural thermal fluctuations are responsible for transitions between these distinct yet transient local aqueous environments in ambient liquid water.

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“…Several schemes to determine whether an H-bond is present or not have been suggested, but the purely geometrical definitions have thus far proven to be insufficiently sensitive. 7 A scheme that provides a bimodal distribution of LDL/HDL local structures, 51,52 when considering the inherent structure 53 of simulated water, is the local structure index 54 (LSI). This order parameter accounts for the structure and coordination of the first and second solvation shells.…”

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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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Growth and collapse of structural patterns in the hydrogen bond network in liquid water

Cited by 161 publications

References 30 publications

Microscopic structure of water at elevated pressures and temperatures

Microscopic structure of water at elevated pressures and temperatures

Local structure analysis in ab initio liquid water

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

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