Hydrogen Bond Structure and Dynamics in Aqueous Electrolytes at Ambient and Supercritical Conditions

Guàrdia, E.; Laría, Daniel; Martı́, Jordi

doi:10.1021/jp056981p

Cited by 99 publications

(110 citation statements)

References 56 publications

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“…The correlation times were reported to be 20 to 50 times longer than those of pure water. MD simulations on halide-water systems suggested that the very long correlation times measured by two-color pump-probe experiments were similar to residence times of water molecules in the first hydration shells of halide anions in dilute solutions (30,(47)(48)(49). However, there is no bulk water in the highly concentrated salt solutions, and, as shown in previous studies of various water systems (5)(6)(7)18), the FFCFs of water are nonexponential in nature and decays on multiple time scales.…”

Section: Discussionsupporting

confidence: 64%

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Hydrogen bond dynamics in aqueous NaBr solutions

Park

Fayer

2007

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

293

403

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Hydrogen bond dynamics of water in NaBr solutions are studied by using ultrafast 2D IR vibrational echo spectroscopy and polarization-selective IR pump-probe experiments. The hydrogen bond structural dynamics are observed by measuring spectral diffusion of the OD stretching mode of dilute HOD in H2O in a series of high concentration aqueous NaBr solutions with 2D IR vibrational echo spectroscopy. The time evolution of the 2D IR spectra yields frequency-frequency correlation functions, which permit quantitative comparisons of the influence of NaBr concentration on the hydrogen bond dynamics. The results show that the global rearrangement of the hydrogen bond structure, which is represented by the slowest component of the spectral diffusion, slows, and its time constant increases from 1.7 to 4.8 ps as the NaBr concentration increases from pure water to Ϸ6 M NaBr. Orientational relaxation is analyzed with a wobbling-in-a-cone model describing restricted orientational diffusion that is followed by complete orientational randomization described as jump reorientation. The slowest component of the orientational relaxation increases from 2.6 ps (pure water) to 6.7 ps (Ϸ6 M NaBr). Vibrational population relaxation of the OD stretch also slows significantly as the NaBr concentration increases.ultrafast 2D IR spectroscopy ͉ water dynamics in ionic solutions W ater plays an important role in chemical and biological processes. In aqueous solutions, water molecules dissolve ionic compounds, charged chemical species, and biomolecules by forming hydration shells (layers) around them. Pure water undergoes rapid structural evolution of the hydrogen bond network that is responsible for water's unique properties (1). A question of fundamental importance is how the dynamics of water in the immediate vicinity of an ion or ionic group differ from those of pure water. For monatomic ions, molecular ions, charged groups of large molecules, or charged amino acids on the surfaces of proteins, the basic structure of hydration shells is determined by ion-dipole interactions between water molecules and the charged group (2, 3). Such ion-dipole interactions will influence both the structure and dynamics of water in the proximity of ions. Water dynamics in ion hydration shells play a significant role in the nature of systems such as proteins and micelles (3) and in processes such as ion transport through transmembrane proteins (4).Over the last several years, the application of ultrafast IR vibrational echo spectroscopy (5, 6), particularly 2D IR vibrational echo experiments, (7, 8) combined with molecular dynamics (MD) simulations (9-12) have greatly enhanced understanding of the hydrogen bond dynamics in pure water. These experiments directly examine the dynamics of water rather than study the indirect influence of water dynamics on a probe molecule (13). The ultrafast 2D IR vibrational echo experiments on water (7, 8) and other hydrogen-bonded systems (14) build upon earlier IR pump-probe experiments that have been extensively used to study ...

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Section: Discussionsupporting

confidence: 64%

“…Recently, MD simulations performed on ionicsolution, hydrogen-bond lifetime correlation functions were calculated (48,49). These simulations show that the lifetime of water-Br Ϫ hydrogen bonds is a few picoseconds and is somewhat longer than that of water-water hydrogen bonds (49).…”

Section: Discussionmentioning

confidence: 99%

Hydrogen bond dynamics in aqueous NaBr solutions

Park

Fayer

2007

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

293

403

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“…We now mention two other recent studies whose conclusions are broadly in line with those of Omta et al (Omta et al, 2003). Guardia et al (Guardia et al, 2006) carried out extensive molecular dynamics simulations of aqueous alkali metal and halides at ambient and supercritical conditions to explore the effects of ions on the intermolecular connectivity of water in the close vicinity of solutes. From a dynamical perspective, the most relevant feature was that the lifetimes of hydrogen bond do not seem to be affected in an appreciable manner by the presence of ions.…”

Section: Structure Of Water Near Ionssupporting

confidence: 63%

Hydrogen Bond Interactions Between Water Molecules in Bulk Liquid, Near Electrode Surfaces and Around Ions

Rastogi¹,

Ghosh²,

Suresh³

2011

Thermodynamics - Physical Chemistry of Aqueous Systems

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“…At this point it has to be mentioned that very similar geometric criteria have been successfully used in the past to predict the HB properties of water and alcohols 9,[31][32][33][34][35][36][37][38][39][40][41][42][43] . Using this simple geometric criterion, the calculated average number of hydrogen bonds per water molecule < n HB > has been estimated to be 3.48, in agreement with the value of 3.58 obtained by reverse modelling of neutron diffraction data 44 .…”

Section: A Local Structure -Hb Networkmentioning

confidence: 99%

Hydrogen Bonding and Related Properties in Liquid Water: A Car–Parrinello Molecular Dynamics Simulation Study

2014

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The local hydrogen bonding structure and dynamics of liquid water have been investigated using the Car-Parrinello molecular dynamics simulation technique. The radial distribution functions and coordination numbers around water molecules have been found to be strongly dependent on the number of hydrogen bonds formed by each molecule, revealing also the existence of local structural heterogeneities in the structure of the liquid. The results obtained have also revealed the strong effect of the local hydrogen bonding network on the local tetrahedral structure and entropy. The investigation of the dynamics of the local hydrogen bonding network in liquid water has shown that this network is very labile and the hydrogen bonds break and reform very rapidly. Nevertheless, it has been found that the hydrogen bonding states associated with the formation of 4 hydrogen bonds by a water molecule exhibit the largest survival probability and corresponding lifetime. The reorientational motions of water molecules have also been found to be strongly dependent on their initial hydrogen bonding state.Finally the dependence of the librational and vibrational modes of water molecules on the local hydrogen bonding network has been carefully examined, revealing a significant effect upon the libration and bond-stretching peak frequencies. The calculated low frequency peaks come in agreement with previously reported interpretations of the experimental low frequency Raman spectrum of liquid water.

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Hydrogen Bond Structure and Dynamics in Aqueous Electrolytes at Ambient and Supercritical Conditions

Cited by 99 publications

References 56 publications

Hydrogen bond dynamics in aqueous NaBr solutions

Hydrogen bond dynamics in aqueous NaBr solutions

Hydrogen Bond Interactions Between Water Molecules in Bulk Liquid, Near Electrode Surfaces and Around Ions

Hydrogen Bonding and Related Properties in Liquid Water: A Car–Parrinello Molecular Dynamics Simulation Study

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