On the accurate calculation of the dielectric constant from molecular dynamics simulations: The case of SPC/E and SWM4-DP water

Gereben, Orsolya; Pusztai, László

doi:10.1016/j.cplett.2011.02.064

Cited by 104 publications

(110 citation statements)

References 29 publications

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“…Previous work has shown the importance of selecting the appropriate block length for the correct calculation of this property of water [94,95]. This is confirmed by the results shown in Fig.…”

Section: The Static Dielectric Constantsupporting

confidence: 80%

Molecular dynamics simulations for the prediction of the dielectric spectra of alcohols, glycols and monoethanolamine

Cardona

Fartaria

Sweatman

et al. 2015

Molecular Simulation

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This version is available at https://strathprints.strath.ac.uk/54062/ Strathprints is designed to allow users to access the research output of the University of Strathclyde. Unless otherwise explicitly stated on the manuscript, Copyright © and Moral Rights for the papers on this site are retained by the individual authors and/or other copyright owners. Please check the manuscript for details of any other licences that may have been applied. You may not engage in further distribution of the material for any profitmaking activities or any commercial gain. You may freely distribute both the url (https://strathprints.strath.ac.uk/) and the content of this paper for research or private study, educational, or not-for-profit purposes without prior permission or charge.Any correspondence concerning this service should be sent to the The response of molecular systems to electromagnetic radiation in the microwave region (0.3-300 GHz) has been principally studied experimentally, using broadband dielectric spectroscopy. However, relaxation times corresponding to reorganisation of molecular dipoles due to their interaction with electromagnetic radiation at microwave frequencies are within the scope of modern molecular simulations. In this work, fluctuations of the total dipole moment of a molecular system, obtained through molecular dynamics simulations, are used to determine the dielectric spectra of water, a series of alcohols and glycols, and monoethanolamine. Although the force fields employed in this study have principally been developed to describe thermodynamic properties, most them give fairly good predictions of this dynamical property for these systems. However, the inaccuracy of some models and the long simulation times required for the accurate estimation of the static dielectric constant can sometimes be problematic. We show that the use of the experimental value for the static dielectric constant in the calculations, instead of the one predicted by the different models, yields satisfactory results for the dielectric spectra, and hence the heat absorbed from microwaves, avoiding the need for extraordinarily long simulations or re-calibration of molecular models.

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Section: The Static Dielectric Constantsupporting

confidence: 80%

Molecular dynamics simulations for the prediction of the dielectric spectra of alcohols, glycols and monoethanolamine

Cardona

Fartaria

Sweatman

et al. 2015

Molecular Simulation

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“…(5), 87 where M is the total dipole of the whole system and the high frequency dielectric constant ε ∞ is estimated from the Clausius-Mossotti equation. 88 As noticed before, 26,89 unlike other liquid properties, the evaluation of ε requires an extended simulation time for convergence ( Figure S4 in the supplementary material 40 ) and the convergence profiles obtained here are very similar to that presented for the SPC/E model as studied by Gereben and Pusztai, 89…”

Section: E Bulk Phasesupporting

confidence: 60%

Six-site polarizable model of water based on the classical Drude oscillator

Lopes

Roux

et al. 2013

The Journal of Chemical Physics

117

151

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A polarizable water model, SWM6, was developed and optimized for liquid phase simulations under ambient conditions. Building upon the previously developed SWM4-NDP model, additional sites representing oxygen lone-pairs were introduced. The geometry of the sites is assumed to be rigid. Considering the large number of adjustable parameters, simulated annealing together with polynomial fitting was used to facilitate model optimization. The new water model was shown to yield the correct self-diffusion coefficient after taking the system size effect into account, and the dimer geometry is better reproduced than in the SWM4 models. Moreover, the experimental oxygen-oxygen radial distribution is better reproduced, indicating that the new model more accurately describes the local hydrogen bonding structure of bulk phase water. This was further validated by its ability to reproduce the experimental nuclear magnetic shielding and related chemical shift of the water hydrogen in the bulk phase, a property sensitive to the local hydrogen bonding structure. In addition, comparison of the liquid properties of the SWM6 model is made with those of a number of widely used additive and polarizable models. Overall, improved balance between the description of monomer, dimer, clustered, and bulk phase water is obtained with the new model compared to its SWM4-NDP polarizable predecessor, though application of the model requires an approximately twofold increase on computational resources.

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“…We considered heavy instead of light water for computational efficiency (use of a larger time step in MD simulations). According to empirical MD studies (34,51) and our DFT-MD tests at ∼1 GPa and 1,000 K H 2 O, the isotopic effect is negligible on dielectric constant calculations. The density of water mentioned in the main text is for H 2 O.…”

Section: Methodsmentioning

confidence: 99%

“…1. For example, at ambient conditions, Gereben and Pusztai (34) showed that trajectories of several nanoseconds are required to obtain converged values of e 0 , which are unaffordable using ab initio MD. However, within the T range of the Earth's mantle, water molecules diffuse and rotate much faster than at ambient conditions: The diffusion coefficient of water at 0.88 g/cm and 1,000 K is about one order of magnitude larger than that at ambient conditions, and this makes it possible to compute e 0 over picosecond-long trajectories.…”

Section: Equation Ofmentioning

confidence: 99%

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.

182

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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On the accurate calculation of the dielectric constant from molecular dynamics simulations: The case of SPC/E and SWM4-DP water

Cited by 104 publications

References 29 publications

Molecular dynamics simulations for the prediction of the dielectric spectra of alcohols, glycols and monoethanolamine

Molecular dynamics simulations for the prediction of the dielectric spectra of alcohols, glycols and monoethanolamine

Six-site polarizable model of water based on the classical Drude oscillator

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

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