The solvation of Na+ in water: First-principles simulations

White, Jeremy; Schwegler, Eric; Galli, Giulia; Gygi, François

doi:10.1063/1.1288688

Cited by 253 publications

(267 citation statements)

References 35 publications

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“…8 If the nature of the donor hydrogen bonds is not significantly affected by dissolved Na + ions, as indicated by these ab initio MD results, 8 and also the direct electronic perturbation by Na + ions is small, as we have shown above, then the presence of Na + ions in liquid water consequently has almost no effect on the observed XA spectrum. Therefore, the changes to the liquid water XA spectrum upon NaCl addition are determined principally by interactions between the Cl -ion and water molecules.…”

Section: Discussionmentioning

confidence: 72%

The Electronic Structure of the Hydrated Proton: A Comparative X-ray Absorption Study of Aqueous HCl and NaCl Solutions

et al. 2005

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The oxygen K edge X-ray absorption spectra of aqueous HCl and NaCl solutions reveal distinct perturbations of the local water molecules by the respective solutes. While the addition of NaCl leads to large spectral changes, the effect of HCl on the observed X-ray absorption spectrum is surprisingly small. Density functional theory calculations suggest that this difference primarily reflects a strong blue shift of the hydrated proton (in either the Eigen (H 9 O 4 + ) or Zundel (H 2 O 5 + ) forms) spectrum relative to that of H 2 O, indicating the tighter binding of electrons in H 3 O + . This spectral shift counteracts the spectral changes that arise from direct electrostatic perturbation of water molecules in the first solvation shell of Cl -. Consequently, the observed spectral changes effected by HCl addition are minimal compared to those engendered by NaCl. Additionally, these results indicate that the effect of monovalent cations on the nature of the unoccupied orbitals of water molecules in the first solvation shell is negligible, in contrast to the large effects of monovalent anions.

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Section: Discussionmentioning

confidence: 72%

The Electronic Structure of the Hydrated Proton: A Comparative X-ray Absorption Study of Aqueous HCl and NaCl Solutions

et al. 2005

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“…33 However, the distribution of angles from classical MD simulations (such as the one used here to obtain the cluster geometries) tends to be strongly peaked at 180°and decreases to near zero by 90°, although the details depend importantly on the particular simulation force field used. 24,33,39,40 Thus, the orientation of water molecules with respect to the cation in the clusters used here (obtained from classical MD simulations) may not provide a completely accurate representation of the relative orientations between the diValent cations and the solvating water molecules. However, these calculations should provide a reasonable first approximation of the direct electronic perturbation by the divalent cations.…”

Section: Discussionmentioning

confidence: 91%

Effects of Cations on the Hydrogen Bond Network of Liquid Water: New Results from X-ray Absorption Spectroscopy of Liquid Microjets

et al. 2006

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Oxygen K-edge X-ray absorption spectra (XAS) of aqueous chloride solutions have been measured for Li + , Na + , K + , NH 4 + , C(NH 2 ) 3 + , Mg 2+ , and Ca 2+ at 2 and 4 M cation concentrations. Marked changes in the liquid water XAS are observed upon addition of the various monovalent cation chlorides that are nearly independent of the identity of the cation. This indicates that interactions with the dissolved monovalent cations do not significantly perturb the unoccupied molecular orbitals of water molecules in the vicinity of the cations and that water-chloride interactions are primarily responsible for the observed spectral changes. In contrast, the addition of the divalent cations engenders changes unique from the case of the monovalent cations, as well as from each other. Density functional theory calculations suggest that the ion-specific spectral variations arise primarily from direct electronic perturbation of the unoccupied orbitals due to the presence of the ions, probably as a result of differences in charge transfer from the water molecules onto the divalent cations.

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“…[10][11][12] Inclusion of the chloride anion was motivated by the need to compare directly to experimental X-ray absorption spectra. It is not universally agreed upon whether the Cl -ion itself imparts any specific changes to the features of the XAS of different solutions.…”

Section: Resultsmentioning

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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The solvation of Na+ in water: First-principles simulations

Cited by 253 publications

References 35 publications

The Electronic Structure of the Hydrated Proton: A Comparative X-ray Absorption Study of Aqueous HCl and NaCl Solutions

The Electronic Structure of the Hydrated Proton: A Comparative X-ray Absorption Study of Aqueous HCl and NaCl Solutions

Effects of Cations on the Hydrogen Bond Network of Liquid Water: New Results from X-ray Absorption Spectroscopy of Liquid Microjets

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

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