The interatomic structure of water at supercritical temperatures

Postorino, P.; Tromp, R. Hans; Ricci, Maria Antonietta; Soper, A. K.; Neilson, G. W.

doi:10.1038/366668a0

Cited by 260 publications

(154 citation statements)

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“…This was in contrast to partial correlation functions derived from simulation using popular two-body and polarizable water force fields, which exhibit a persistence of hydrogen-bonding to much higher temperatures 28,50,174,175 . This stimulated much debate and constructive interplay between simulation and further experimental studies that eventually and clearly indicated that hydrogenbonding persists to temperatures well beyond the original neutron scattering estimate [46][47][48][49]103,171 .…”

Section: Water Structure Away From Ambient Conditionsmentioning

confidence: 99%

“…partial correlation functions at one supercritical state point of T=673K and ρ=0.66g/ml, and showed the disappearance of the hydrogen-bonding peak in g OH (r) 50,74 . This was in contrast to partial correlation functions derived from simulation using popular two-body and polarizable water force fields, which exhibit a persistence of hydrogen-bonding to much higher temperatures 28,50,174,175 .…”

Section: Water Structure Away From Ambient Conditionsmentioning

confidence: 99%

“…We therefore devote considerable space in this review to the procedures of scattering data acquisition, data reduction, and analysis in x-ray and neutron scattering. At the same time this exposure allows for appreciation of the fundamental difficulties of these experiments, and the important progress made by the experimental community over the last 25 years to improve the quality of scattering data on liquid water, not only under ambient conditions as recently reported by our own group 40,41 , but in different thermodynamic regimes such as supercooled [42][43][44][45] or supercritical [46][47][48][49][50] , in confined geometries 51 , or in aqueous solutions of biochemical or chemical importance. 13,23,[52][53][54][55][56][57][58][59] This review also measures the progress in the simulation of liquid water structure.…”

Section: Introductionmentioning

confidence: 99%

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Water Structure from Scattering Experiments and Simulation

2002

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Section: Water Structure Away From Ambient Conditionsmentioning

confidence: 99%

Section: Water Structure Away From Ambient Conditionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Water Structure from Scattering Experiments and Simulation

2002

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“…The same technique has been used by Gorbatyi and Demyanets 2 to obtain the RDF of water in a wide temperature range of 298-773 K and at a pressure of 1000 bar. Soper et al 3,4 have reported the RDF of water from 298 to 673 K at various pressures, which includes both sub-and supercritical water states, using neutron diffraction technique.…”

Section: Introductionmentioning

confidence: 99%

“…A variety of experimental data for water g(r) are available in the literature, which are obtained by means of X-ray and neutron diffraction techniques. [1][2][3][4] The Fourier transform of the (g(r) -1), which is generally named as the structure factor, 5 has been measured for saturated liquid water in a wide temperature range of 298-473 K by Narten and Levy 1 using an X-ray diffraction technique. The same technique has been used by Gorbatyi and Demyanets 2 to obtain the RDF of water in a wide temperature range of 298-773 K and at a pressure of 1000 bar.…”

Section: Introductionmentioning

confidence: 99%

Application of Integral Equation Joined with the Chain Association Theory to Study Molecular Association in Sub- and Supercritical Water

2001

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Abstract:In this report, the Percus-Yevick and the Ornestein-Zernike integral equations are solved simultaneously for the radial distribution functions of water at various state conditions, including sub-and supercritical states. The intermolecular potential function used in this study consists of an effective Kihara potential, which is derived for associated fluids. For derivation of the effective potential function, water is considered as a mixture of associated species due to hydrogen bonding. The contribution of hydrogen bonding is considered in the formulation of the effective Kihara potential parameters through the application of the analytic chain association theory. There is a good agreement between the present calculations and the experimental data in predicting the oxygen-oxygen radial distribution function near the critical point and at supercritical conditions for which experimental data are available. It is also concluded that at supercritical conditions a considerable degree of hydrogen bonding may be still present in the form of linear chain association. Therefore, the chain association model is valid near the critical point and at supercritical conditions instead of other structure models for the investigations on molecular structure of water.calculations, they ignored the temperature dependency of the intermolecular distances between the nearest neighboring molecules.On the basis of the reported experimental data, 2 it is evident that the intermolecular distances between the nearest neighbors are temperature-dependent. Then this temperature dependency should be accounted for in the potential function to be used in the RDF calculations. In this work, the complete form of the effective Kihara potential function, which includes the parameters for the temperature dependency of the nearest neighbors, is used to calculate the RDF (oxygen-oxygen radial distribution function) for water molecules. The method of RDF calculations in this work is based on the application of the integral equation, which, as the results obtained indicate, can be considered as an accurate approach and leads to evaluating the RDF in the whole range of intermolecular distance variations. Also, a new set of constants for the parameters of an effective Kihara potential function is proposed.From a structural viewpoint, the results of these calculations substantiate the previous conclusion by the other workers 2,7,9 that at supercritical conditions, hydrogen bonding in the form of linear chain associations exists between water molecules. In eq 1, R is the polarizability factor, µ is the dipole moment, and σ are energy and size parameters, and r is the intermolecular separation. In this potential function, the dielectric property of pure water has been noted, and the dielectric dipole moment (µ 4 /3kT) and induced dipole (2µ 2 R) terms have been introduced in the intermolecular potential function. This equation is used in our RDF calculations. The results (Figure 1) indicate is another alternative to represent the intermolecular pote...

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Supercritical Water and Aqueous Solutions: Molecular Simulation

Chialvo

Cummings

1998

Encyclopedia of Computational Chemistry

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The interatomic structure of water at supercritical temperatures

Cited by 260 publications

References 11 publications

Water Structure from Scattering Experiments and Simulation

Water Structure from Scattering Experiments and Simulation

Application of Integral Equation Joined with the Chain Association Theory to Study Molecular Association in Sub- and Supercritical Water

Supercritical Water and Aqueous Solutions: Molecular Simulation

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