Temperature Dependence of Hydrogen Bonding in Supercritical Water

Mizan, Tahmid I.; Savage, Phillip E.; Ziff, Robert M.

doi:10.1021/jp951561t

Cited by 171 publications

(97 citation statements)

References 25 publications

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“…Similar hydrogen bonding structure and the hydration of Cl -in hydrothermal NaCl solutions were also quantitatively addressed by experimental (IR and Raman) and computational (classical MD) approaches [35]. They found that the feature of the NaCl structure has a considerable as observed by previous studies for H-bonds (the lifetime of H-bonds in supercritical water is 0.2-0.5 ps [36,37]; see reviews by [38]). The total number of H-bonds increases as a function of density, consistent with the trends observed in Figures 4(a) and 5(a).…”

Section: Hydrogenmentioning

confidence: 56%

CuCl Complexation in the Vapor Phase: Insights from Ab Initio Molecular Dynamics Simulations

et al. 2018

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We investigated the hydration of the CuCl 0 complex in HCl-bearing water vapor at 350 ∘ C and a vapor-like fluid density between 0.02 and 0.09 g/cm 3 using ab initio molecular dynamics (MD) simulations. The simulations reveal that one water molecule is strongly bonded to Cu(I) (first coordination shell), forming a linear [H 2 O-Cu-Cl] 0 moiety. The second hydration shell is highly dynamic in nature, and individual configurations have short life-spans in such low-density vapors, resulting in large fluctuations in instantaneous hydration numbers over a timescale of picoseconds. The average hydration number in the second shell (m) increased from ∼0.5 to ∼3.5 and the calculated number of hydrogen bonds per water molecule increased from 0.09 to 0.25 when fluid density (which is correlated to water activity) increased from 0.02 to 0.09 g/cm 3 ( H 2 O 1.72 to 2.05). These changes of hydration number are qualitatively consistent with previous solubility studies under similar conditions, although the absolute hydration numbers from MD were much lower than the values inferred by correlating experimental Cu fugacity with water fugacity. This could be due to the uncertainties in the MD simulations and uncertainty in the estimation of the fugacity coefficients for these highly nonideal "vapors" in the experiments. Our study provides the first theoretical confirmation that beyond-first-shell hydrated metal complexes play an important role in metal transport in low-density hydrothermal fluids, even if it is highly disordered and dynamic in nature.

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Section: Hydrogenmentioning

confidence: 56%

CuCl Complexation in the Vapor Phase: Insights from Ab Initio Molecular Dynamics Simulations

et al. 2018

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“…Nevertheless, calculation of a basic dynamic characteristic of hydrogen bonding, namely average HB lifetime, was performed by several authors only. In the studies [20,21], calculations were made for a few series of T, P, and q, but these disembodied results did not allow to make up a general picture of average HB lifetime as a function of state parameters. Thus, we found appropriate to perform comprehensive study of HB lifetime dependence on temperature and density in a wide region on state diagram.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen bond lifetime in supercritical water

Петренко

Антипова

2011

Struct Chem

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“…Structural properties of SCW have been extensively studied using different experimental procedures [3][4][5][6][7][8][9] as well as computer simulation with different molecular models. [10][11][12][13][14][15][16][17][18] A central aspect in this discussion is the change in the hydrogen bond network compared to the situation in normal water. There is a reduction in the number of hydrogen bonds 8 and the tetrahedral ordering of the water molecules, a characteristic of the ambient conditions, is missing in the supercritical regime where the density is decreased.…”

Section: Introductionmentioning

confidence: 99%

The isotropic nuclear magnetic shielding constants of acetone in supercritical water: A sequential Monte Carlo/quantum mechanics study including solute polarization

Fonseca

Coutinho²,

Canuto³

2008

The Journal of Chemical Physics

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Monte Carlo simulation strategies for computing the wetting properties of fluids at geometrically rough surfaces J. Chem. Phys. 135, 184702 (2011) Semi-bottom-up coarse graining of water based on microscopic simulations J. Chem. Phys. 135, 184101 (2011) Hydrophobic interactions in presence of osmolytes urea and trimethylamine-N-oxide J. Chem. Phys. 135, 174501 (2011) Potential of mean force between identical charged nanoparticles immersed in a size-asymmetric monovalent electrolyte J. Chem. Phys. 135, 164705 (2011) Additional information on J. Chem. Phys. The nuclear isotropic shielding constants ͑ 17 O͒ and ͑ 13 C͒ of the carbonyl bond of acetone in water at supercritical ͑P = 340.2 atm and T = 673 K͒ and normal water conditions have been studied theoretically using Monte Carlo simulation and quantum mechanics calculations based on the B3LYP/ 6-311+ + G͑2d ,2p͒ method. Statistically uncorrelated configurations have been obtained from Monte Carlo simulations with unpolarized and in-solution polarized solute. The results show that solvent effects on the shielding constants have a significant contribution of the electrostatic interactions and that quantitative estimates for solvent shifts of shielding constants can be obtained modeling the water molecules by point charges ͑electrostatic embedding͒. In supercritical water, there is a decrease in the magnitude of ͑ 13 C͒ but a sizable increase in the magnitude of ͑ 17 O͒ when compared with the results obtained in normal water. It is found that the influence of the solute polarization is mild in the supercritical regime but it is particularly important for ͑ 17 O͒ in normal water and its shielding effect reflects the increase in the average number of hydrogen bonds between acetone and water. Changing the solvent environment from normal to supercritical water condition, the B3LYP/ 6-311+ + G͑2d ,2p͒ calculations on the statistically uncorrelated configurations sampled from the Monte Carlo simulation give a 13 C chemical shift of 11.7Ϯ 0.6 ppm for polarized acetone in good agreement with the experimentally inferred result of 9 -11 ppm.

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Temperature Dependence of Hydrogen Bonding in Supercritical Water

Cited by 171 publications

References 25 publications

CuCl Complexation in the Vapor Phase: Insights from Ab Initio Molecular Dynamics Simulations

CuCl Complexation in the Vapor Phase: Insights from Ab Initio Molecular Dynamics Simulations

Hydrogen bond lifetime in supercritical water

The isotropic nuclear magnetic shielding constants of acetone in supercritical water: A sequential Monte Carlo/quantum mechanics study including solute polarization

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