Calculation of near-edge x-ray-absorption fine structure at finite temperatures: Spectral signatures of hydrogen bond breaking in liquid water

Hetényi, Balázs; Angelis, Filippo De; Giannozzi, Paolo; Car, Roberto

doi:10.1063/1.1703526

Cited by 148 publications

(105 citation statements)

References 42 publications

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“…For water, this issue has been discussed, [8][9][10]57,62 and it has been concluded that exciting half an electron, i.e. using the half-core-hole (HCH) approach, provides the best balance between initial and final state effects.…”

Section: A Transition-potential Density Functional Theorymentioning

confidence: 99%

“…Other schemes of categorizing the MD snapshots include, e.g., topological definitions 55 and theoretical energy decomposition approaches. 56 In terms of spectrum calculations, improvements are needed to meet the above mentioned 6 challenges since the theoretical studies conducted to date experience a number of discrepancies when compared to experimental data, e.g., too narrow absorption band, 8,9,36,43,[56][57][58] insufficient pre-edge intensity, 7,39,43,59 and insufficient post-edge intensity. 41,58 Pinpointing the sources of these discrepancies for any specific study is not trivial, since they could be the result of inaccurate core-excitation methods, improper structures, too small cluster or unit cell for core-excitation calculations, or other effects.…”

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confidence: 99%

“…Particularly interesting in this respect are methods based on density functional theory (DFT), amongst which especially the transition-potential DFT (TP-DFT) method 60 has been used extensively for calculations of water X-ray absorption spectra. 2,[7][8][9][10]21,26,30,43,44,57,59,[61][62][63] What is needed is to establish whether TP-DFT, and in particular the workhorse of optical DFT-based spectrum calculations, i.e. time-dependent DFT 64 (TDDFT), can produce results of sufficiently good quality to correlate spectral features to molecular structures.…”

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confidence: 99%

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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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Section: A Transition-potential Density Functional Theorymentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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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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“…This confirmed the experimental analysis in terms of coordination and furthermore lead to an operational H-bond definition relative to a geometrical cone at each of the donor hydrogens which gives the distortion needed to give the pre-and main-edge features and which was used to evaluate MD simulation models. Considering the importance of the theoretical models for the analysis and the results for the full core-hole potential as used by Hetenyi et al 4 we must critically evaluate the approach taken in ref. 1 to compute theoretical XAS spectra in this context.…”

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confidence: 99%

“…This behaviour is also evident if the theoretical spectra of ref. 4 are compared with the experimental data in ref. 1 .…”

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Half or full core hole in density functional theory X-ray absorption spectrum calculations of water?

Cavalleri

Odelius

Nordlund

et al. 2005

Phys. Chem. Chem. Phys.

111

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It was recently suggested, based on x-ray absorption (XAS) and x-ray Raman spectroscopy (XRS) combined with Density Functional Theory (DFT) calculations of spectra, that water in the liquid is in an asymmetric hydrogen bonding situation with only two strong H-bonds: one donating and one accepting with the remaining bonds weakened or broken through mainly bending off the H-bond angle 1 . This provocative result has attracted much attention and debate in the literature. Smith et al. 2 analyzed the temperature dependence of XAS spectra obtained on a liquid microjet and claimed agreement with fourcoordinated water. Their experimental data has, however, been shown to be flawed by saturation effects which invalidate their conclusions 3 . On the theory side Hetenyi et al. 4 computed spectra directly from their ab initio molecular dynamics (AIMD) simulations and claimed agreement with experiment by using a full core hole (FCH) in their spectrum calculations rather than the standard half core hole (HCH). In view of the predominance (80% at room temperature) of single-donor (SD) species reported in ref. 1 this is a surprising and contradictory result with respect to the XAS conclusions since the AIMD simulation only contained 19% SD species being instead dominated by doubledonor (DD), ice-like coordination. In view of the present debate on the structure of water it is important to analyze in depth the validity of the HCH and FCH approximations to the core-hole potential in DFT calculations of XAS spectra. XAS (elsewhere also NEXAFS or XANES) 5 and the corresponding non-resonant x-ray Raman spectroscopy (XRS) 6 are well-established experimental techniques that have recently been extended to measurements of the local electronic structure of liquid water 1,7-11 . Both XAS and XRS show major differences in the spectral profiles between bulk ice and liquid water 1,8,9 ; there is a well-defined pre-edge structure that can be seen in the spectrum of the liquid and is substantially reduced in the bulk ice spectrum; the remaining intensity is mainly due to proton disorder and minor defects 12 . The liquid water spectrum, with strong pre-edge (535 eV) and main-edge (537 eV) features, instead closely resembles that of the ice surface where a dominant fraction of the water molecules in the first half-bilayer has one free O-H bond 1,13 . The spectrum of bulk ice, in which each molecule is tetrahedrally coordinated, is instead characterized by weak main edge (537 eV) and strong post edge (540 eV) features 1,8 ; these experimental differences already indicate that the liquid cannot be dominated by fully coordinated molecules. In ref. 1 density functional theory (DFT) based spectrum calculations using the standard transition potential or HCH approximation were used to interpolate spectra between the two experimental extremes, i.e. bulk and surface of ice. This confirmed the experimental analysis in terms of coordination and furthermore lead to an operational H-bond definition relative to a geometrical cone at each of the donor hydrogens...

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X‐Ray Spectroscopy Calculations within Kohn–Sham DFT: Theory and Applications

Leetmaa

Ljungberg

Nilsson

et al. 2009

Computational Methods in Catalysis and Materials Science

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Calculation of near-edge x-ray-absorption fine structure at finite temperatures: Spectral signatures of hydrogen bond breaking in liquid water

Cited by 148 publications

References 42 publications

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

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

Half or full core hole in density functional theory X-ray absorption spectrum calculations of water?

X‐Ray Spectroscopy Calculations within Kohn–Sham DFT: Theory and Applications

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