A Database for the Static Dielectric Constant of Water and Steam

Fernández, Diego P.; Mulev, Yu. V.; Goodwin, Anthony R. H.; Sengers, J. V.

doi:10.1063/1.555977

Cited by 247 publications

(160 citation statements)

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“…2 shows how e 0 varies with the density and pressure at 1,000 K. For both ab initio and empirical (SPC/E) simulations, e 0 monotonically depends on the density at fixed temperature. When the temperature rises from 1,000 K to 2,000 K, e 0 decreases by about 70% along an isobar, whereas with P increasing from ∼1 GPa to ∼11 GPa, e 0 increases by only about 2.5 times at 1,000 K. The same trend is also found in Fernández et al's experimental database (9), showing that the static dielectric constant of water is more sensitive to temperature along an isobar than to pressure along an isotherm. In Eq.…”

Section: Equation Ofsupporting

confidence: 72%

“…Fig. 1 shows the dielectric constant of water obtained by ab initio MD as a function of the simulation time at ∼1 GPa and 1,000 K. We compared our results with those of the database compiled by Fernández et al (9), which covers the published experimental data until 1995 at P and T up to 1.2 GPa and 873 K, and extrapolated data up to 1 GPa and 1,200 K (13). Our ab initio MD simulations predict a static dielectric constant of ∼15 at 0.88 g/cm 3 , a value that is between those reported by Fernández et al at 0.85 and 0.90 g/cm 3 (Fig.…”

Section: Equation Ofmentioning

confidence: 91%

See 1 more Smart Citation

Dielectric properties of water under extreme conditions and transport of carbonates in the deep Earth

Pan¹,

Spanu²,

Harrison

et al. 2013

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

175

150

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Water is a major component of fluids in the Earth's mantle, where its properties are substantially different from those at ambient conditions. At the pressures and temperatures of the mantle, experiments on aqueous fluids are challenging, and several fundamental properties of water are poorly known; e.g., its dielectric constant has not been measured. This lack of knowledge of water dielectric properties greatly limits our ability to model water-rock interactions and, in general, our understanding of aqueous fluids below the Earth's crust. Using ab initio molecular dynamics, we computed the dielectric constant of water under the conditions of the Earth's upper mantle, and we predicted the solubility products of carbonate minerals. We found that MgCO 3 (magnesite)-insoluble in water under ambient conditions-becomes at least slightly soluble at the bottom of the upper mantle, suggesting that water may transport significant quantities of oxidized carbon. Our results suggest that aqueous carbonates could leave the subducting lithosphere during dehydration reactions and could be injected into the overlying lithosphere. The Earth's deep carbon could possibly be recycled through aqueous transport on a large scale through subduction zones.water solvation properties | carbon cycle | ab initio simulations | supercritical water W ater, a major component of fluids in the Earth's mantle (1, 2), is expected to play a substantial role in hydrothermal reactions occurring in the deep Earth at supercritical conditions (3, 4). Pressure (P) and temperature (T) increase with increasing depth (5) and at ∼400 km, where seismic discontinuities define the bottom boundary of the upper mantle, the pressure can reach ∼13 GPa and the temperature can be as high as 1,700 K (6-8). In this regime the properties of water and thus of aqueous fluids are remarkably different from those at ambient conditions. For example, water has an unusually large static dielectric constant e 0 ∼ 78 at ambient conditions; however, at the vapor-liquid critical point at 647 K, e 0 deceases to less than 10 (9), implying that ionwater interactions in solution are greatly modified. In turn these changes affect the solubility of minerals and hence chemical reactions occurring in aqueous solutions under pressure (10, 11).Measurements of the dielectric constant of water date back to the 1890s (12), but they are still limited to P < 0.5 GPa and T < 900 K, corresponding to crustal metamorphic conditions. Indeed, it is challenging to measure e 0 at high P and T because water becomes highly corrosive (11). Several models correlating experimental data suggested extrapolations of e 0 to ∼1 GPa and ∼1,300 K (e.g., refs. 13-15), which corresponds to only very shallow mantle conditions under the oceans; however, deeper mantle conditions relevant to plate tectonic processes could not be reached and different extrapolations showed poor agreement with each other (1). The current lack of knowledge of the dielectric constant of water under the P and T of the mantle hampers our ability...

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Section: Equation Ofsupporting

confidence: 72%

Section: Equation Ofmentioning

confidence: 91%

Dielectric properties of water under extreme conditions and transport of carbonates in the deep Earth

Pan¹,

Spanu²,

Harrison

et al. 2013

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

175

150

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show abstract

“…experiments on moist air in the visible [3,9,18,53 [42,61,79] and eventually in the static limit [24], the refractive index plotted as a function of wavelength is more and more structured by individual lines. Since we will not present these functions at high resolution but smooth fits within several bands in the infrared, their spiky appearance sets a natural limit to the far-IR wavelength regions that our approach may cover.…”

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confidence: 99%

Refractive index of humid air in the infrared: model fits

Mathar¹

2007

J. Opt. A: Pure Appl. Opt.

103

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The theory of summation of electromagnetic line transitions is used to tabulate the Taylor expansion of the refractive index of humid air over the basic independent parameters (temperature, pressure, humidity, wavelength) in five separate infrared regions from the H to the Q band at a fixed percentage of Carbon Dioxide. These are least-squares fits to raw, highly resolved spectra for a set of temperatures from 10 to 25 • C, a set of pressures from 500 to 1023 hPa, and a set of relative humidities from 5 to 60%. These choices reflect the prospective application to characterize ambient air at mountain altitudes of astronomical telescopes. The paper provides easy access to predictions of the refractive index of humid air at conditions that are typical in atmospheric physics, in support of ray tracing [5] and astronomical applications [4,16,47,50] until experimental coverage of the infrared wavelengths might render these obsolete. The approach is in continuation of earlier work [46] based on a more recent HITRAN database [60] plus more precise accounting of various electromagnetic effects for the dielectric response of dilute gases, as described below.The literature of optical, chemical and atmospheric physics on the subject of the refractive index of moist air falls into several categories, sorted with respect to decreasing relevance (if relevance is measured by the closeness to experimental data and the degree of independence to the formalism employed here):1. experiments on moist air in the visible [3,9,18,53 [42,61,79] and eventually in the static limit [24], the refractive index plotted as a function of wavelength is more and more structured by individual lines. Since we will not present these functions at high resolution but smooth fits within several bands in the infrared, their spiky appearance sets a natural limit to the far-IR wavelength regions that our approach may cover. II. DIELECTRIC MODEL A. MethodologyThe complex valued dielectric function n(ω) of air n = 1 +χ (1) is constructed from molecular dynamical polarizabilitiesN m are molecular number densities, S ml are the line intensities for the transitions enumerated by l. ω 0ml are the transition angular frequencies, Γ ml the full linewidths at half maximum. c is the velocity of light in vacuum, and i the imaginary unit. The line shape (2) adheres to the complex-conjugate symmetry χ m (ω) = χ * m (−ω), as required for functions which are real-valued in the time domain. The sign convention of Γ ml merely reflects a sign choice in the Fourier Transforms and carries no real significance; a sign in the Kramers-Kronig formulas is bound to it. The integrated imaginary part is [28] whereν = k/(2π) = ω/(2πc) = 1/λ is the wavenumber.

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“…A large diversity of molecular models are available for liquid water (Guillot 2002;Hess and van der Vegt 2006). Nevertheless, it seems difficult to obtain a model able to reproduce its static dielectric constant (78.43 ± 0.10 at room temperature) (Fernández et al 1995). Only a quite few commonly used water molecular models have recently achieved a reasonable reproduction of its dielectric constant [e.g., Dill's SPC/DC model (78.3 ± 6), (Fennell et al 2012) Barbosa's TIP4P/ (78.3), (Fuentes-Azcatl and Barbosa 2016) Roux & MacKerell's polarizable water model (78.1) (Yu et al 2013)] although the adequacy of their combination with available biomolecular force fields remains to be investigated.…”

Section: Introductionmentioning

confidence: 99%

Development of constant-pH simulation methods in implicit solvent and applications in biomolecular systems

daSilva

Dias

2017

Biophys Rev

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pH is a critical parameter for biological and technological systems directly related with electrical charges. It can give rise to peculiar electrostatic phenomena, which also makes them more challenging. Due to the quantum nature of the process, involving the forming and breaking of chemical bonds, quantum methods should ideally by employed. Nevertheless, due to the very large number of ionizable sites, different macromolecular conformations, salt conditions, and all other charged species, the CPU time cost simply becomes prohibitive for computer simulations, making this a quite complex problem. Simplified methods based on Monte Carlo sampling have been devised and will be reviewed here, highlighting the updated state-ofthe-art of this field, advantages, and limitations of different theoretical protocols for biomolecular systems (proteins and nucleic acids). Following a historical perspective, the discussion will be associated with the applications to protein interactions with other proteins, polyelectrolytes, and nanoparticles.

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A Database for the Static Dielectric Constant of Water and Steam

Cited by 247 publications

References 2 publications

Dielectric properties of water under extreme conditions and transport of carbonates in the deep Earth

Dielectric properties of water under extreme conditions and transport of carbonates in the deep Earth

Refractive index of humid air in the infrared: model fits

Development of constant-pH simulation methods in implicit solvent and applications in biomolecular systems

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