Submit to Minerals Review for Minerals Propose a Special Issue

Journal Menu

Journal Browser

► Journal Browser

Molecular Simulation of Mineral-Solution Interfaces

Print Special Issue Flyer
Special Issue Editors
Special Issue Information
Keywords
Published Papers

A special issue of Minerals (ISSN 2075-163X).

Deadline for manuscript submissions: closed (6 April 2018) | Viewed by 50665

Share This Special Issue

Special Issue Editor

Dr. Andrey G. Kalinichev

E-Mail Website
Guest Editor

Laboratoire SUBATECH, UMR 6457–Institut Mines-Télécom Atlantique, Université de Nantes, CNRS/IN2P3, 44307 Nantes, France
Interests: computational molecular modeling of mineral-water interfaces and confined aqueous phases in clay, cement, and other nano-strucutred materials; environmental materials chemistry; geological nuclear waste disposal; physical chemistry of soil organic matter
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

With the dramatic supercomputing hardware and software progress over the last 10–20 years, the geochemical research community is becoming more and more interested in the application of computational molecular modeling techniques for the studies of minerals and mineral-solution interfaces in order to solve a wide variety of important geochemical, mineralogical, and environmental problems.

Most geochemical reactions involve fluid phases and take place at mineral–fluid interfaces or in confined spaces of mineral interlayers and nanopores. These reactions affect many important natural and technological processes controlling mineral weathering and dissolution; adsorption and release of environmental contaminants in soil and water; the fate of CO₂ in geological carbon sequestration; flotation and other mineral processing technologies; long-term stability and safety of geological nuclear waste repositories; enhanced oil and gas recovery from unconventional sources, etc. Fundamental molecular-scale understanding of the chemistry and physics involved in all these processes is essential.

We invite contributions to this Special Issue on all aspects of molecular simulation of mineral-solution interfaces using various modeling techniques from quantum ab initio, to classical force field based molecular dynamics (MD) and Monte Carlo (MC) methods, to mesoscale coarse grained simulations, etc. Contributions making direct links between atomistic computer simulations of mineral-solution interfaces and molecular scale experimental studies, such as synchrotron X-ray, neutron scattering, and other surface-sensitive techniques, are espeically encouraged.

Dr. Andrey G. Kalinichev
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Minerals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

Computer simulations
Molecular dynamics
Monte Carlo
Mineral-solution interfaces
Nano-confined water in minerals
Adsorption
Diffusion
Intercalation
Swelling

Published Papers (10 papers)

Download All Papers

Research

12 pages, 4753 KiB

Open AccessArticle

Water Adsorption on the β-Dicalcium Silicate Surface from DFT Simulations

by Qianqian Wang, Hegoi Manzano, Iñigo López-Arbeloa and Xiaodong Shen

Minerals 2018, 8(9), 386; https://doi.org/10.3390/min8090386 - 04 Sep 2018

Cited by 23 | Viewed by 4284

Abstract

β-dicalcium silicate (β-Ca₂SiO₄ or β-C₂S in cement chemistry notation) is one of the most important minerals in cement. An improvement of its hydration rate would be the key point for developing environmentally-friendly cements with lower energy consumption and CO₂ emissions. However, there is a lack of fundamental understanding on the water/β-C₂S surface interactions. In this work, we aim to evaluate the water adsorption on three β-C₂S surfaces at the atomic scale using density functional theory (DFT) calculations. Our results indicate that thermodynamically favorable water adsorption takes place in several surface sites with a broad range of adsorption energies (−0.78 to −1.48 eV) depending on the particular mineral surface and adsorption site. To clarify the key factor governing the adsorption of the electronic properties of water at the surface were analyzed. The partial density of states (DOS), charge analysis, and electron density difference analyses suggest a dual interaction of water with a β-C₂S (100) surface including a nucleophilic interaction of the water oxygen lone pair with surface calcium atoms and an electrophilic interaction (hydrogen bond) of one water hydrogen with surface oxygen atoms. Despite the elucidation of the adsorption mechanism, no correlation was found between the electronic structure and the adsorption energies. Full article

(This article belongs to the Special Issue Molecular Simulation of Mineral-Solution Interfaces)

► Show Figures

Graphical abstract

16 pages, 548 KiB

Open AccessEditor’s ChoiceArticle

What the Diffuse Layer (DL) Reveals in Non-Linear SFG Spectroscopy

by Simone Pezzotti, Daria Ruth Galimberti, Y. Ron Shen and Marie-Pierre Gaigeot

Minerals 2018, 8(7), 305; https://doi.org/10.3390/min8070305 - 20 Jul 2018

Cited by 27 | Viewed by 4293

Abstract

Following our recent work [Phys. Chem. Chem. Phys. 20:5190–99 (2018)] that provided the means to unambigously define and extract the three water regions at any charged interface (solid–liquid and air–liquid alike), denoted the BIL (Binding Interfacial Layer), DL (Diffuse Layer) and Bulk, and [...] Read more.

χ^{2} (ω)

spectroscopic contributions from Density Functional Theory (DFT)-based ab initio molecular dynamics simulations (DFT-MD/AIMD), we show here that the

χ_{D L}^{2} (ω)

signal arising from the DL water region carries a wealth of essential information on the microscopic and macroscopic properties of interfaces. We show that the

χ_{D L}^{2} (ω)

signal carries information on the surface potential and surface charge, the isoelectric point, EDL (Electric Double Layer) formation, and the relationship between a nominal electrolyte solution pH and surface hydroxylation state. This work is based on DFT-MD/AIMD simulations on a (0001)

α

–quartz–water interface and on the air–water interface, with various surface quartz hydroxylation states and various electrolyte concentrations. The conclusions drawn make use of the interplay between experiments and simulations. Most of the properties listed above can now be extracted from experimental

χ_{D L}^{2} (ω)

alone with the protocols given in this work, or by making use of the interplay between experiments and simulations, as described in this work. Full article

(This article belongs to the Special Issue Molecular Simulation of Mineral-Solution Interfaces)

► Show Figures

Figure 1

16 pages, 1425 KiB

Open AccessEditor’s ChoiceArticle

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

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

Minerals 2018, 8(5), 205; https://doi.org/10.3390/min8050205 - 10 May 2018

Cited by 10 | Viewed by 4783

Abstract

Following our previous works on dioctahedral clays, we extend the classical Polarizable Ion Model (PIM) to trioctahedral clays, by considering dry Na-, Cs-, Ca- and Sr-hectorites as well as hydrated Na-hectorite. The parameters of the force field are determined by optimizing the atomic forces and dipoles on density functional theory calculations. The simulation results are validated by comparison with experimental X-ray diffraction (XRD) data. The XRD patterns calculated from classical molecular dynamics simulations performed with the PIM force field are in very good agreement with experimental results. In the bihydrated state, the less structured electronic density profile obtained with PIM compared to the one from the state-of-the-art non-polarizable force field clayFF explains the slightly better agreement between the PIM results and experiments. Full article

(This article belongs to the Special Issue Molecular Simulation of Mineral-Solution Interfaces)

► Show Figures

Figure 1

10 pages, 1588 KiB

Open AccessArticle

Molecular Simulation of Minerals-Asphalt Interfacial Interaction

by Daisong Luo, Meng Guo and Yiqiu Tan

Minerals 2018, 8(5), 176; https://doi.org/10.3390/min8050176 - 24 Apr 2018

Cited by 28 | Viewed by 3851

Abstract

The interfacial interaction between asphalt binder and mineral aggregate makes different components have different diffusion behavior. It influences the performance of interface and consequently that of the mix. In this research, the models of four asphalt components (asphaltene, resin, aromatics and saturate) and five minerals were constructed individually, and then the Al₂O₃-asphalt interface model was constructed by adding the asphalt layer and mineral layer together. The interfacial behavior at molecular scale was simulated by setting boundary conditions, optimizing the structure and canonical ensemble. The mean square displacement (MSD) and diffusion coefficient of particles were selected as indicators to study the diffusion of asphalt components on the surface of Al₂O₃. The results show that when the temperature was 65 °C, asphalt binder showed more viscosity, the diffusion speed of asphalt components ranked according to their molecular mass, which was saturate > aromatics > resin > asphaltene. At 25 °C and 165 °C, the resin had the fastest diffusion speed, which was nearly twice of asphaltene. The interaction between asphalt components and Al₂O₃ mineral surface can make the diffusion of asphalt components independent on temperature. Full article

(This article belongs to the Special Issue Molecular Simulation of Mineral-Solution Interfaces)

► Show Figures

Figure 1

25 pages, 77723 KiB

Open AccessArticle

Crystal Dissolution Kinetics Studied by a Combination of Monte Carlo and Voronoi Methods

by Ricarda D. Rohlfs, Cornelius Fischer, Inna Kurganskaya and Andreas Luttge

Minerals 2018, 8(4), 133; https://doi.org/10.3390/min8040133 - 24 Mar 2018

Cited by 12 | Viewed by 4717

Abstract

Kinetic Monte Carlo (kMC) methods have been used extensively for the study of crystal dissolution kinetics and surface reactivity. A current restriction of kMC simulation calculations is their limitation in spatial system size. Here, we explore a new and very fast method for the calculation of the reaction kinetics of a dissolving crystal, capable of being used for much larger systems. This method includes a geometrical approach, the Voronoi distance map, to generate the surface morphology, including etch pit evolution, and calculation of reaction rate maps and rate spectra in an efficient way, at a calculation time that was about 1/180 of the time required for a kMC simulation of the same system size at one million removed atoms. We calculate Voronoi distance maps that are based on a distance metric corresponding to the crystal lattice, weighted additively in relation to stochastic etch pit depths. We also show how Voronoi distance maps can be effectively parameterized by kMC simulation results. The resulting temporal sequences of Voronoi maps provide kinetic information. By comparing temporal sequences of kMC simulation and Voronoi distance maps of identical etch pit distributions, we demonstrate the opportunity of making specific predictions about the dissolution reaction kinetics, based on rate maps and rate spectra. The dissolution of an initially flat Kossel crystal surface served as an example to show that a sequence of Voronoi calculations can predict dissolution kinetics based on the information about the distribution of screw defects. The results confirm that a geometrical relationship exists between the material flux from the surface at a certain point and the distance (or, when considering anisotropy, a function of distance) to the nearest defect. In this study, for the sake of comparability, the calculations are made using input parameters directly derived from the kMC models operating at the atomic scale. We show that, using values of v(r_pit) and weighting factors obtained by kMC, the resulting surface morphologies and material flux are almost identical. This implies that discrete Voronoi calculations of starting and end points of the dissolution are sufficient to calculate material flux maps, without the time-consuming overhead of computing the interim reactions at the atomic-scale. This opens a promising new venue to efficiently upscale full-atomic kMC models to the continuum macroscopic level where reactive transport and Lattice Boltzmann calculations can be applied. Full article

(This article belongs to the Special Issue Molecular Simulation of Mineral-Solution Interfaces)

► Show Figures

Figure 1

18 pages, 12570 KiB

Open AccessArticle

Density Functional Theory Study of Arsenate Adsorption onto Alumina Surfaces

by Katie W. Corum, Ali Abbaspour Tamijani and Sara E. Mason

Minerals 2018, 8(3), 91; https://doi.org/10.3390/min8030091 - 01 Mar 2018

Cited by 21 | Viewed by 7329

Abstract

Atomistic modeling of mineral–water interfaces offers a way of confirming (or refuting) experimental information about structure and reactivity. Molecular-level understanding, such as orbital-based descriptions of bonding, can be developed from charge density and electronic structure analysis. First-principles calculations can be used to identify weaknesses in empirical models. This provides direction on how to propose more robust representations of systems of increasing size that accurately represent the underlying physical factors governing reactivity. In this study, inner-sphere complex geometries of arsenate on hydrated alumina surfaces are modeled at the density functional theory (DFT)–continuum solvent level. According to experimental studies, arsenate binds to alumina surfaces in a bidentate binuclear (BB) fashion. While the DFT calculations support the preference of the BB configuration, the optimized geometries show distortion from the ideal tetrahedral geometry of the arsenic atom. This finding suggests that steric factors, and not just coordination arguments, influences reactivity. The O_surf–As–O_surf angle for the more favorable arsenate configurations is closest to the ideal tetrahedral angle of 109.5°. Comparing the results of arsenate adsorption using a small cluster model with a periodic slab model, we report that the two model geometries yield results that differ qualitatively and quantitatively. This relates the steric factors and rigidity of the surface models. Full article

(This article belongs to the Special Issue Molecular Simulation of Mineral-Solution Interfaces)

► Show Figures

Figure 1

13 pages, 4560 KiB

Open AccessArticle

Molecular Modeling of Adsorption of 5-Aminosalicylic Acid in the Halloysite Nanotube

by Ana Borrego-Sánchez, Mahmoud E. Awad and Claro Ignacio Sainz-Díaz

Minerals 2018, 8(2), 61; https://doi.org/10.3390/min8020061 - 11 Feb 2018

Cited by 14 | Viewed by 5013

Abstract

Halloysite nanotubes are becoming interesting materials for drug delivery. The knowledge of surface interactions is important for optimizing this application. The aim of this work is to perform a computational study of the interaction between 5-aminosalicylic acid (5-ASA) drug and halloysite nanotubes for the development of modified drug delivery systems. The optimization of this nanotube and the adsorption of different conformers of the 5-ASA drug on the internal surface of halloysite in the presence and absence of water were performed using quantum mechanical calculations by using Density Functional Theory (DFT) and methods based on atomistic force fields for molecular modeling, respectively. Full article

(This article belongs to the Special Issue Molecular Simulation of Mineral-Solution Interfaces)

► Show Figures

Graphical abstract

16 pages, 8258 KiB

Open AccessArticle

Structural and Electronic Properties of Different Terminations for Quartz (001) Surfaces as Well as Water Molecule Adsorption on It: A First-Principles Study

by Xianchen Wang, Qin Zhang, Xianbo Li, Junjian Ye and Longjiang Li

Minerals 2018, 8(2), 58; https://doi.org/10.3390/min8020058 - 09 Feb 2018

Cited by 30 | Viewed by 6682

Abstract

Structural and electronic properties of Si termination, O-middle termination, and O-rich terminations of a quartz (001) surface as well as water molecule adsorption on it were simulated by means of density functional theory (DFT). Calculated results show that the O-middle termination exposing a single oxygen atom on the surface is the most stable model of quartz (001) surface, with the lowest surface energy at 1.969 J·m⁻², followed by the O-rich termination and Si termination at 2.892 J·m⁻² and 2.896 J·m⁻², respectively. The surface properties of different terminations mainly depend on the surface-exposed silicon and oxygen atoms, as almost all the contributions to the Fermi level (E_F) in density of states (DOS) are offered by the surface-exposed atoms, especially the O2p state. In the molecular adsorption model, H₂O prefers to adsorb on the surface Si and O atoms, mainly via O₁–H₁ bond at 1.259 Å and Si₁–O_w at 1.970 Å by Van der Waals force and weak hydrogen bond with an adsorption energy of −57.89 kJ·mol⁻¹. In the dissociative adsorption model, the O-middle termination is hydroxylated after adsorption, generating two new Si–OH silanol groups on the surface and forming the O_wH₂···O₄ hydrogen bond at a length of 2.690 Å, along with a large adsorption energy of −99.37 kJ·mol⁻¹. These variations in the presence of H₂O may have a great influence on the subsequent interfacial reactions on the quartz surface. Full article

(This article belongs to the Special Issue Molecular Simulation of Mineral-Solution Interfaces)

► Show Figures

Graphical abstract

8747 KiB

Open AccessArticle

New Insights into the Adsorption of Oleate on Cassiterite: A DFT Study

by Jie Liu, Guichen Gong, Yuexin Han and Yimin Zhu

Minerals 2017, 7(12), 236; https://doi.org/10.3390/min7120236 - 27 Nov 2017

Cited by 24 | Viewed by 4322

Abstract

A new understanding of the adsorption mechanism of oleate on cassiterite surfaces is presented by density functional theory (DFT) calculations. Various convergence tests were conducted to optimize the parameter settings for the rational simulation of cassiterite bulk unit cell and surface slabs. The calculated surface energies of four low-index cassiterite cleavage planes form an increasing sequence of (110) < (100) < (101) < (001), demonstrating (110) is the most thermodynamically stable surface of cassiterite. The interaction strengths of the oleate ion (OL⁻), OH⁻, and H₂O on the SnO₂ (110) face are in the order of H₂O < OH⁻ < OL⁻, which reveals that the OL⁻ is able to replace the adsorbed H₂O and OH⁻ on the mineral surfaces. Mulliken population calculations and electron density difference analysis show that electrons transfer from the Sn atoms on the cassiterite (110) surface to the O atoms offered by carboxyl groups of oleate during the interaction. The populations of newly formed O1–Sn1 and O2–Sn2 bonds are 0.30 and 0.29, respectively, indicating that these two bonds are of a very low covalency. Density of states analysis reveals that the formation of an O1–Sn1 bond mainly results from the 5s and 5p orbitals of the Sn1 atom and the 2p orbital of the O1 atom. Full article

(This article belongs to the Special Issue Molecular Simulation of Mineral-Solution Interfaces)

► Show Figures

Figure 1

9739 KiB

Open AccessArticle

In Situ Investigation of the Adsorption of Styrene Phosphonic Acid on Cassiterite (110) Surface by Molecular Modeling

by Guichen Gong, Yuexin Han, Jie Liu, Yimin Zhu, Yanfeng Li and Shuai Yuan

Minerals 2017, 7(10), 181; https://doi.org/10.3390/min7100181 - 27 Sep 2017

Cited by 19 | Viewed by 3997

Abstract

Abstract: The flotation, adsorption and bonding mechanisms of styrene phosphonic acid (SPA) to cassiterite were studied using microflotation tests, zeta potential measurements, solution chemistry analysis and density functional theory (DFT) calculations in this paper. Flotation results demonstrated SPA was an excellent collector for cassiterite which could recover over 85% cassiterite particles with the pH range 4.3–6.06 and 40 mg/L SPA. Zeta potential measurements and solution chemistry analysis revealed the adsorption of SPA was mainly contributed by the chemisorption of the monoanions on cassiterite surfaces. Frontier molecular orbital theory analysis and adsorption energy calculation results proved the monoanion of SPA was able to replace the OH⁻ on cassiterite surfaces. The adsorption structure optimization results confirmed the binuclear complex was the most favorable adsorption configuration of SPA on cassiterite (110) surface. Mulliken population calculations and density of states analysis indicated during the bonding process the Sn3 atom lost electrons to O3 atom, and the bonding interaction between O3 and Sn3 atoms was mainly from the contribution of the 2p orbital of O3 atom and the 5s and 5p orbitals of Sn3 atom. Full article

(This article belongs to the Special Issue Molecular Simulation of Mineral-Solution Interfaces)

► Show Figures

Figure 1

Journal Menu

Journal Browser

Molecular Simulation of Mineral-Solution Interfaces

Share This Special Issue

Special Issue Editor

Special Issue Information

Keywords

Published Papers (10 papers)

Research

Further Information

Guidelines

MDPI Initiatives

Follow MDPI