Development and application of ReaxFF methodology for understanding the chemical dynamics of metal carbonates in aqueous solutions

Dasgupta, Nabankur; Chen, Chen; Duin, Adri C. T. van

doi:10.1039/d1cp04790f

Cited by 27 publications

(19 citation statements)

References 47 publications

(61 reference statements)

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“…The systems in Figure undergo equilibrium simulations with the ReaxFF force field, as detailed in the computational methods section of the Supporting Information (SI). After equilibration, the free energy calculations are performed using well-tempered metadynamics, available in the COLVARS package built in the LAMMPS software .…”

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confidence: 99%

Hydrophobic Nanoconfinement Enhances CO₂ Conversion to H₂CO₃

Dasgupta

Rempe

et al. 2023

J. Phys. Chem. Lett.

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Understanding the formation of H2CO3 in water from CO2 is important in environmental and industrial processes. Although numerous investigations have studied this reaction, the conversion of CO2 to H2CO3 in nanopores, and how it differs from that in bulk water, has not been understood. We use ReaxFF metadynamics molecular simulations to demonstrate striking differences in the free energy of CO2 conversion to H2CO3 in bulk and nanoconfined aqueous environments. We find that nanoconfinement not only reduces the energy barrier but also reverses the reaction from endothermic in bulk water to exothermic in nanoconfined water. Also, charged intermediates are observed more often under nanoconfinement than in bulk water. Stronger solvation and more favorable proton transfer with increasing nanoconfinement enhance the thermodynamics and kinetics of the reaction. Our results provide a detailed mechanistic understanding of an important step in the carbonation process, which depends intricately on confinement, surface chemistry, and CO2 concentration.

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confidence: 99%

Hydrophobic Nanoconfinement Enhances CO₂ Conversion to H₂CO₃

Dasgupta

Rempe

et al. 2023

J. Phys. Chem. Lett.

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“…The systems in Fig. 1 undergo equilibrium simulations with the ReaxFF force field, [68] as detailed in the computational methods section of the supporting information (SI). After equilibration, the free energy calculations are performed using well-tempered metadynamics, [71] available in the COLVARS [72] package built in the LAMMPS software package.…”

Section: Resultsmentioning

confidence: 99%

“…ReaxFF force fields are parameterized according to DFT data and are capable of accurately defining bond formation and bond breaking in large systems (> 10 6 atoms). [65][66][67][68][69] When combined with an enhanced sampling method, ReaxFF molecular simulations can sample high energy states of a relatively large chemically reactive system that would not be possible using ab initio or non-reactive molecular simulations. [70] Therefore, for the present study, ReaxFF metadynamics molecular simulation is deemed to be a reasonable approach for understanding the kinetics and thermodynamics of H2CO3 formation in clay interlayers, and comparing with the reaction in the bulk, which has already been studied extensively in the past.…”

Section: Introductionmentioning

confidence: 99%

Hydrophobic nanoconfinement enhances CO2 conversion to H2CO3

Dasgupta

Rempe

et al. 2022

Preprint

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An understanding of the formation of H2CO3 in water from carbon dioxide is important in many environmental, biological, and industrial processes, and in the global carbon cycle. Although numerous computational and experimental investigations have focused on understanding these interactions, the conversion of CO2 to H2CO3 in nanopores, and how this conversion differs from that in bulk water, has not been understood. In this study, we use ReaxFF metadynamics molecular simulations to demonstrate striking differences in the free energy of CO2 conversion to H2CO3 in bulk water compared with that in water confined in pyrophyllite nanopores. We find that the nanoconfinement not only reduces the energy barrier, but also reverses the reaction from endothermic in bulk water to exothermic in nanoconfined water. In addition, charged species are observed more often under nanoconfinement than in bulk water. The higher number of reactive encounters, stronger solvation, and more favorable proton transfer with increasing confinement enhance the thermodynamics and kinetics of the reaction. As carbonation in nanopores is important in the carbon cycle and a complicated problem that depends on confinement, surface chemistry, pore chemistry, and concentration of CO2, our results provide a mechanistic understanding to an important step in this process.

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“…In particular, proton transfer is coupled strongly with CaCO 3 precipitation; bicarbonate (

{\mathrm{H}\mathrm{C}\mathrm{O}}_{{3}^{-}}

) is the dominant species in the environmental‐pH solution, whereas the crystal minerals only contain carbonate (

{\mathrm{C}\mathrm{O}}_{3}^{2-}

). Although reactive FFs, for example, ReaxFF, [115,116] can lift such a restriction by correlating the interaction potential with atomic distances and bond orders, they have yet to be validated for mineral–water interfaces and are thus not sufficiently accurate for quantitative studies.…”

Section: Methodsmentioning

confidence: 99%

Atomistic simulations of nucleation and growth of CaCO₃ with the influence of inhibitors: A review

Li,

Zeng,

Zhang

2023

Materials Genome Engineering Advances

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Calcium carbonate (CaCO3) is a crucial mineral with great scientific relevance in biomineralization and geoscience. However, excessive precipitation of CaCO3 is posing a threat to industrial production and the aquatic environment. The utilization of chemical inhibitors is typically considered an economical and successful route for addressing the scaling issues, while the underlying mechanism is still debated and needs to be further investigated. In this context, a deep understanding of the crystallization process of CaCO3 and how the inhibitors interact with CaCO3 nuclei and crystals are of great significance in evaluating the performance of scale inhibitors. In recent years, with the rapid development of computing facilities, computer simulations have provided an atomic‐level perspective on the kinetics and thermodynamics of possible association events in CaCO3 solutions as well as the predictions of nucleation pathway and growth mechanism of CaCO3 crystals as a complement to experiment. This review surveys several computational methods and their achievements in this field with a focus on analyzing the functional mechanisms of different types of inhibitors. A general discussion of the current challenges and future directions in applying atomistic simulations to the discovery, design, and development of more effective water‐scale inhibitors is also discussed.

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Development and application of ReaxFF methodology for understanding the chemical dynamics of metal carbonates in aqueous solutions

Abstract: A new ReaxFF reactive force field has been developed for metal carbonate systems including Na+, Ca2+, and Mg2+ cations and the CO32- anion. This force field is fully transferable with...

Cited by 27 publications

References 47 publications

Hydrophobic Nanoconfinement Enhances CO₂ Conversion to H₂CO₃

Hydrophobic Nanoconfinement Enhances CO₂ Conversion to H₂CO₃

Hydrophobic nanoconfinement enhances CO2 conversion to H2CO3

Atomistic simulations of nucleation and growth of CaCO₃ with the influence of inhibitors: A review

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Development and application of ReaxFF methodology for understanding the chemical dynamics of metal carbonates in aqueous solutions

Abstract: A new ReaxFF reactive force field has been developed for metal carbonate systems including Na+, Ca2+, and Mg2+ cations and the CO32- anion. This force field is fully transferable with...

Cited by 27 publications

References 47 publications

Hydrophobic Nanoconfinement Enhances CO2 Conversion to H2CO3

Hydrophobic Nanoconfinement Enhances CO2 Conversion to H2CO3

Hydrophobic nanoconfinement enhances CO2 conversion to H2CO3

Atomistic simulations of nucleation and growth of CaCO3 with the influence of inhibitors: A review

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Hydrophobic Nanoconfinement Enhances CO₂ Conversion to H₂CO₃

Hydrophobic Nanoconfinement Enhances CO₂ Conversion to H₂CO₃

Atomistic simulations of nucleation and growth of CaCO₃ with the influence of inhibitors: A review