Classical Polarizable Force Field to Study Hydrated Hectorite: Optimization on DFT Calculations and Validation against XRD Data

Hånde, Ragnhild; Ramothe, Vivien; Tesson, Stéphane; Dazas, Baptiste; Ferrage, Eric; Lanson, Bruno; Salanne, Mathieu; Rotenberg, Benjamin; Marry, Virginie

doi:10.3390/min8050205

Cited by 12 publications

(18 citation statements)

References 87 publications

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“…However, PIM has already shown a very good agreement with the experiments on the structure of concentrated solutions 47,89 as well as on the structure of clays. [48][49][50][51] We can thus assume that PIM may correctly describe the structure of the species at the interface. To test this assumption, it would be interesting to reproduce this study on clays more tractable experimentally, such as muscovites, on which reflectivity studies can be conducted.…”

Section: Resultsmentioning

confidence: 99%

“…PIM was developed initially for the modeling of aqueous electrolytes, 47 and was extended more recently to include the parameters necessary to model various clay minerals and zeolites. [48][49][50][51] In this force field each atom is treated as a polarizable charged ball.…”

Section: Molecular Dynamics Force Fieldsmentioning

confidence: 99%

“…[41][42][43][44][45][46] The consideration of polarizability at montmorillonite surface/water interfaces improved also significantly the quantitative agreement of MD predictions of interlayer space structure with XRD experimental results. [47][48][49][50][51] However, this improvement was obtained at a significant numerical cost, and the necessity to include polarizability in clay/water MD simulations must be then evaluated as a function of the system properties of interest. In this study, we evaluated the influence of four different combinations of polarizable and non-polarizable force fields on the prediction of the structure and dynamics of water and ions in a mesopore (width 50Å) containing a NaCl aqueous solutions and bordered with Na-montmorillonite surfaces.…”

Section: Introductionmentioning

confidence: 99%

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Influence of Polarizability on the Prediction of the Electrical Double Layer Structure in a Clay Mesopore: A Molecular Dynamics Study

et al. 2020

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The prediction of the water and ion density profiles in the electrical double layer (EDL) is a key insight for macroscopic models that intend to model transport and swelling properties in clay materials. Unfortunately, the structure of the EDL, and especially the ion distribution, cannot be probed directly by measurements, because EDL features are inherently disturbed by direct measurement techniques. In recent years, Molecular Dynamics have provided a growing set of information on the properties of the EDL, including the properties of the diffuse layer, located beyond the Stern or compact layer, and in which a diffuse cloud of ions screens the remaining uncompensated surface charge. Molecular Dynamics results are, however, dependent on the force field used to run the simulations. In this study, we investigated the influence of the choice of a force field on the structural and dynamic properties of the EDL present at montmorillonite surface/water interfaces in a 50Å wide slit-shaped mesopore. Simulations were run in the presence and in the absence of added NaCl, and the results were compared to ion distributions in the diffuse layer predicted with a Poisson-Boltzmann model. The simulations evidenced the strong influence of the consideration of polarizability of ions and water molecules on the predicted structural and dynamic properties of the EDL. While non polarizable force fields gave results in good agreement with the prediction of the Poisson-Boltzmann theory, our tested polarizable force field, PIM, showed very significant deviations, which could be mainly attributed to the enhanced formation of ion pairs.

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Section: Resultsmentioning

confidence: 99%

Section: Molecular Dynamics Force Fieldsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Influence of Polarizability on the Prediction of the Electrical Double Layer Structure in a Clay Mesopore: A Molecular Dynamics Study

et al. 2020

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“…H-bonding plays a crucial role in their properties, either in their interactions with water 17,[22][23][24][25] or, in the case of so-called 1:1 clays whose layers comprise an H-bond donating and an H-bond accepting sheet, in the cohesive forces holding these layers together 13,26,27 . Theoretical studies have been carried out at multiple scales, from quantum-mechanical calculations intended to find the ground-state structure of clays and characterize the types of H-bonding [27][28][29][30][31][32] to molecular dynamics simulations, either using ab initio descriptions of the electron structure to study clay wetting 14,24 or acidbase chemistry 33,34 or larger-scale studies with classical forcefields 26,35 to model diffraction 36 or vibrational spectroscopy 37 experiments.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen-bonding and nuclear quantum effects in clays

Kurapothula

Shepherd

Wilkins

2022

The Journal of Chemical Physics

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Hydrogen bonds are of paramount importance in the chemistry of clays, mediating the interaction between the clay surface and water, and for some materials between separate layers. It is well-established that the accuracy of a computational model for clays depends on the level of theory at which the electronic structure is treated. However, for hydrogen-bonded systems, the motion of light H nuclei on the electronic potential energy surface is often affected by quantum delocalization. Using path integral molecular dynamics, we show that nuclear quantum effects lead to a relatively small change in the structure of clays, but one that is comparable to the variation incurred by treating the clay at different levels of electronic structure theory. Accounting for quantum effects weakens the hydrogen bonds in clays, with H-bonds between different layers of the clay affected more than those within the same layer; this is ascribed to the fact that the confinement of an H atom inside a layer is independent of its participation in hydrogen-bonding. More importantly, the weakening of hydrogen bonds by nuclear quantum effects causes changes in the vibrational spectra of these systems, significantly shifting the O–H stretching peaks and meaning that in order to fully understand these spectra by computational modeling, both electronic and nuclear quantum effects must be included. We show that after reparameterization of the popular clay forcefield CLAYFF, the O–H stretching region of their vibrational spectra better matches the experimental one, with no detriment to the model’s agreement with other experimental properties.

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Section: Introductionmentioning

confidence: 99%

Hydrogen Bonding and Nuclear Quantum Effects in Clays

Kurapothula,

Shepherd,

Wilkins

2021

Preprint

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Hydrogen bonds are of paramount importance in the chemistry of clays, mediating the interaction between the clay surface and water, and for some materials between separate layers. It is well-established that the accuracy of a computational model for clays depends on the level of theory at which the electronic structure is treated. However, for hydrogen-bonded systems the motion of light H nuclei on the electronic potential energy surface is often affected by quantum delocalization. Using path integral molecular dynamics, we show that nuclear quantum effects lead to a relatively small change in the structure of clays, but one that is comparable to the variation incurred by treating the clay at different levels of electronic structure theory. Accounting for quantum effects weakens the hydrogen bonds in clays, with H-bonds between different layers of the clay affected more than those within the same layer; this is ascribed to the fact that the confinement of an H atom inside a layer is independent of its participation in hydrogen-bonding. More importantly, the weakening of hydrogen bonds by nuclear quantum effects causes changes in the vibrational spectra of these systems, significantly shifting the O-H stretching peaks and meaning that in order to fully understand these spectra by computational modelling, both electronic and nuclear quantum effects must be included. We show that after reparametrization of the popular CLAYFF model for clays, the O-H stretching region of their vibrational spectra better matches the experimental one, with no detriment to the model's agreement with other experimental properties.

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Classical Polarizable Force Field to Study Hydrated Hectorite: Optimization on DFT Calculations and Validation against XRD Data

Cited by 12 publications

References 87 publications

Influence of Polarizability on the Prediction of the Electrical Double Layer Structure in a Clay Mesopore: A Molecular Dynamics Study

Influence of Polarizability on the Prediction of the Electrical Double Layer Structure in a Clay Mesopore: A Molecular Dynamics Study

Hydrogen-bonding and nuclear quantum effects in clays

Hydrogen Bonding and Nuclear Quantum Effects in Clays

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