Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge

Schreck, Simon; Wernet, Philippe

doi:10.1063/1.4962237

Cited by 19 publications

(30 citation statements)

References 61 publications

(122 reference statements)

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“…[4][5][6][7] Recently, the high-resolution oxygen K-edge core-level spectroscopy, such as X-ray absorption spectra (XAS) and X-ray Raman scattering, has emerged as a powerful experimental technique to probe the electronic structure and infer the molecular structure of water and ice, as well as aqueous solutions. 6,[8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] Excited from the oxygen 1s core level, the electron excitation probes the unoccupied electronic states, which are anti-bonding along the covalent OH bonds and particularly sensitive to the HBs. Therefore, the XAS technique serves as a local probe for the HB structures of liquid water and ice.…”

Section: Introductionmentioning

confidence: 99%

“…11,18,[20][21][22] Experimentally, the pre-edge feature is present in both liquid water and ice but is more intense in the former. The relative intensities between main-edge and post-edge of liquid water and crystalline ice Ih are substantially different.…”

Section: Introductionmentioning

confidence: 99%

“…The relative intensities between main-edge and post-edge of liquid water and crystalline ice Ih are substantially different. 6,[8][9][10][11][20][21][22][23][24] As one of the most qualitative differences, the intensity of main-edge is higher than that of the post-edge in the XAS of liquid water, while the opposite trend is true for the spectra in the ice.…”

Section: Introductionmentioning

confidence: 99%

“…[65][66][67][68][69][70] However, calculations of the XAS significantly depend on the QWs as they are explicitly involved in the evaluation of the transition matrix elements M ij in Eq. (1 21 A representative snapshot from the PBE0+vdW AIMD trajectory containing 128 water molecules was used for all spectra calculations. The first excitation scheme by GGA-level DFT (blue dashed) with the FCH approximation is a one-step calculation without changing the input wave functions.…”

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confidence: 99%

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X-ray absorption of liquid water by advanced ab initio methods

et al. 2017

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Oxygen K-edge X-ray absorption spectra of liquid water are computed based on the configurations from advanced ab initio molecular dynamics simulations, as well as an electron excitation theory from the GW method. One one hand, the molecular structures of liquid water are accurately predicted by including both van der Waals interactions and hybrid functional (PBE0). On the other hand, the dynamic screening effects on electron excitation are approximately described by the recently developed enhanced static Coulomb hole and screened exchange approximation by Kang and Hybertsen [Phys. Rev. B 82, 195108 (2010)]. The resulting spectra of liquid water are in better quantitative agreement with the experimental spectra due to the softened hydrogen bonds and the slightly broadened spectra originating from the better screening model.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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X-ray absorption of liquid water by advanced ab initio methods

et al. 2017

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“…Under the influence of NQEs, the more delocalized protons are found to introduce an unexpected competing effects in the H-bond network in addition to the softening of liquid structure [37,39,40]. The quantum nuclei has been shown to have important effects on XAS spectrum [41][42][43].…”

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X-ray Absorption Spectral Signature of Quantum Nuclei in Liquid Water

Sun¹,

Zheng²,

Chen³

et al. 2018

Preprint

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Based on electron-hole excitation theory, we investigate the X-ray absorption spectral signature of nuclear quantum effect in liquid water, whose molecular structure is simulated by path-integral molecular dynamics using the MB-pol model. Compared to spectra generated from classically modeled water structure, quantum nuclei has important effect on spectra in terms of both the spectral energies and their line shapes. At the short-range ordering of H-bond network, the delocalized protons increase the fluctuations on the intramolecular covalency and broaden the pre-edge of the spectra. For intermediate-range and long-range orderings, the observed red and blue shifts of the main-edge and post-edge are attributed to the so-called competing quantum effects, under which both the weak and well-formed H-bonds are promoted. The theoretical spectra are in nearly quantitative agreement with the available experimental data.The nature of H-bond network in water continues to be at the center of scientific interests [1][2][3][4][5][6][7][8][9][10][11][12]. Recently, high-resolution X-ray absorption spectroscopy (XAS), has emerged to be a powerful experimental technique to probe the water structure at molecular scale [13][14][15][16][17][18][19]. Allowed by Franck-Condon principle [20], the electrons leaving the oxygen core can be described as excited electronic states from an instantaneously frozen snapshot of water at equilibrium. Therefore, XAS spectrum inherits a unique local signature of its molecular environment, complimentary to the scattering experiments [21,22].Ab initio theory is desired for an unambiguous interpretation of the underlying molecular structure. However, theoretical prediction has posed a major challenge by itself. The computed XAS spectrum is sensitive to the accuracy of methods in both the adopted electronic and molecular theories. Rigorously, the electron-hole excitation theories, such as the Bethe-Salpeter equation (BSE) [13,[23][24][25], should be applied beyond the unoccupied electronic structure from density functional theory [26][27][28][29]. However, the BSE is computational formidable and has not yet widely applied in water. The above computational burden has been greatly alleviated by the recently introduced approximate BSE solution utilizing localized basis [30]. On the other hand, the modeling of water at molecular level is no less difficult. The difficulty lies at the complex nature of the H-bond structure balanced by many physical interactions. The directional H-bond, as the building block of the near-tetrahedral structure in water, is much weaker than the ordinary (covalent or ionic) chemical bond. Furthermore, the H-bond network is largely modified by the van der Waals interaction, whose energy is even weaker than H-bond by one order of magnitude [31][32][33][34][35]. Worse still, nuclear quantum effects (NQEs) should be properly considered due to the low mass of proton [36][37][38]. Under the influence of NQEs, the more delocalized protons are found to introduce an unexpected competing e...

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Physical Methods for the Study of Biological Water—Miscellaneous

Likhtenshtein¹

2021

Biological Water

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Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge

Cited by 19 publications

References 61 publications

X-ray absorption of liquid water by advanced ab initio methods

X-ray absorption of liquid water by advanced ab initio methods

X-ray Absorption Spectral Signature of Quantum Nuclei in Liquid Water

Physical Methods for the Study of Biological Water—Miscellaneous

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