Reactive force fields for modeling oxidative degradation of organic matter in geological formations

Hur, Jaewoong; Abousleiman, Younane N.; Hull, Katherine L.; Qomi, Mohammad Javad Abdolhosseini

doi:10.1039/d1ra04397h

Cited by 7 publications

(16 citation statements)

References 45 publications

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“…Some differences appear at large distances. For chloroethane and chloroethanol, differences appear above 2.6Å, as the results obtained by Hur et al 35 . This can be explained by the overestimation of the Cl-C-H angle.…”

Section: Bond Dissociation Energy and Bond Lengthssupporting

confidence: 83%

“…ReaxFF parameters for the chlorine element were first provided in the Protein-2013 force field where chlorine was included as a counter ion 4 . It was also parameterized in two different force fields to deal with oxidative degradation of organic matter in geological formations 35 and explosive compounds 36 . In both cases, the parameter set is not transferable enough to consider organochloride compounds, particularly for conjugated or aromatic molecules.…”

Section: Please Cite This Article As Doi:101063/50120831mentioning

confidence: 99%

“…The root mean square deviations (RMSD) of the energy differences are 8.36 kcal mol −1 (0.36 eV) and 8.91 kcal mol −1 (0.39 eV in the training set and the validation set, respectively. For comparison, Hur et al 35 obtained a RMSD of the energy of about 1.57 eV for their force field optimized to investigate the degradation of compounds with oxychlorine.…”

Section: A Force Field Validation Against Qm Calculationsmentioning

confidence: 99%

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Development of a novel ReaxFF reactive potential for organochloride molecules

Wolf

Bégué

Vallverdu

2022

The Journal of Chemical Physics

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This article presents a new reactive potential in the ReaxFF formalism. It aims to include the chlorine element, and opens up the fields of use of ReaxFF to the whole class of organochloride compounds including conjugated or aromatic groups. Numerous compounds in this family raise global awareness due to their environmental impact, and such a reactive potential will help investigate their degradation pathways. The new force field belongs to the aqueous branch. The force field parameters were fitted against high-level quantum chemistry calculations, including CASSCF/NEVPT2 calculations and density functional theory calculations, and its accuracy was evaluated using a validation set. The root means square deviation against quantum mechanics energies is 0.38 eV (8.91 kcal/mol). From a structural point of view, the root means square deviation is about 0.06Å for the bond lengths, 11.86{degree sign} for the angles and 4.12{degree sign} for the dihedral angles. With CHONCl-2022_weak new force field, we successfully investigated the regioselectivity for nucleophilic or electrophilic attacks on polychlorinated biphenyls (PCB), which are toxic and permanent pollutants. The rotation barriers along the bond linking the two benzene rings, which is crucial in the toxicity of these compounds, are well reproduced by CHONCl-2022_weak. Then our new reactive potential is used to investigate the chlorobenzene atmospheric oxidation, initiated by a hydroxyl radical. The reaction pathways computed with ReaxFF agree with the quantum mechanics results. We showed that, in the presence of dioxygen molecules, the oxidation of chlorobenzene likely leads to the formation of highly oxygenated compounds after the abstraction of hydrogen radicals.

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Section: Bond Dissociation Energy and Bond Lengthssupporting

confidence: 83%

Section: Please Cite This Article As Doi:101063/50120831mentioning

confidence: 99%

Section: A Force Field Validation Against Qm Calculationsmentioning

confidence: 99%

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Development of a novel ReaxFF reactive potential for organochloride molecules

Wolf

Bégué

Vallverdu

2022

The Journal of Chemical Physics

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“…Historically, they are used as biocide agents and viscosity modifiers in hydraulic fracturing fluids. − More recently, a new type of reactive fracturing fluid was proposed, and its chemical properties enable oxidative degradation of kerogen, a polymer-like intertwined organic material, present in unconventional source rock. This unique reactivity allows for increased hydrocarbon recovery by physically cracking the organic matter and opening conductive channels to enable the flow of hydrocarbons. , Another unique use of oxidizers for potential reservoir stimulation applications is in situ acid generation where bromate (BrO 3 – ) can selectively oxidize ammonium (NH 4 + ) to liberate acid (H + ) yielding a series of inorganic acids …”

Section: Introductionmentioning

confidence: 99%

“…This unique reactivity allows for increased hydrocarbon recovery by physically cracking the organic matter and opening conductive channels to enable the flow of hydrocarbons. 4,5 Another unique use of oxidizers for potential reservoir stimulation applications is in situ acid generation where bromate (BrO 3 − ) can selectively oxidize ammonium (NH 4 + ) to liberate acid (H + ) yielding a series of inorganic acids. 6 Here, we expand the repertoire of acids generated utilizing this versatile redox chemistry approach to include a series of industrially relevant organic acids having a wide range of pK a values.…”

Section: Introductionmentioning

confidence: 99%

Specific-Ion Effects Unveil a Route for Modulating Oxidatively Triggered Acid Systems for Reservoir Applications

2022

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On-demand in situ preparation of industrially relevant organic acids, namely, methanesulfonic acid, triflic acid, and trifluoroacetic acid, is demonstrated in this study. Sodium and potassium bromate were found to selectively oxidize a series of ammonium salts NH4X, where X = OMs, OTf, or OTFAc, with characteristic clock reaction behavior. The redox system undergoes rapid acid formation following an extended induction time at 150 °C and is identified as a potential candidate for high-temperature oil field chemistry applications where on-demand acid placement is required. Although the reaction kinetics for acid formation from NH4X salts where X = Cl, Br, F, or SO4 2– follows a pK a trend, the rates of formation of the organic acids are much slower and deviate from this trend. Furthermore, we demonstrate that the rate of acid formation can be modulated by the addition of alkali metal salts, with the strongest effect observed from LiBr. Spectroscopic studies implicate the formation of lithium bromate ion pairs that slow or altogether inhibit the oxidation of NH4 +. Additionally, the presence of Br– alters the reaction path, eliminating the clock behavior and creating a pathway for Li+ to strongly inhibit the redox reaction. From these studies, a method for slowing ammonium oxidation under reservoir conditions to sufficiently delay acid formation until the precursors are placed in the zone of interest is identified.

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A ReaxFF Potential for Modeling Organic Matter Degradation with Oxybromine Oxidants

Hur,

Abousleiman,

Hull

et al. 2024

ChemPhysChem

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Oxidation of organic matter with oxybromine oxidants is ushering in a new era of enhanced hydrocarbon recovery. While these potent reagents are being tested in laboratory and field experiments, there is a pressing demand to delineate the molecular processes governing oxidation reactions at geological depth. Here, we parameterize a ReaxFF potential to model the oxidative decompositions of aliphatic and aromatic hydrocarbons in the presence of water‐NaBr solutions that contain oxybromine (BrOn)‐ oxidizers. Our parameterization results in a reliable empirical bond‐order potential that accurately calculates bond energies, exhibiting an RMSE of ~1.18 eV, corresponding to 1.36 % average error. Reproducing bond dissociation and binding energies from Density Functional Theory (DFT), our parameterization proves transferable to aqueous environments. This H/C/O/Na/Br ReaxFF potential accurately reproduces the oxidation pathways of small hydrocarbons with oxybromine oxidizers. This force field captures proton and oxygen transfer, C‐C bond tautomerization, and cleavage, leading to ring‐opening and chain fragmentation. Molecular dynamic simulations demonstrate the oxidative degradation of aromatic and aliphatic kerogen‐like moieties in bulk solutions. We envision that such reactive force fields will be useful to understand better the oxidation reactions of organic matter formed in geological reservoirs for enhanced shale gas recovery and improved carbon dioxide treatments.

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Reactive force fields for modeling oxidative degradation of organic matter in geological formations

Abstract: Oxidative degradations of hydrocarbons with ClOn− oxidizers (n = 1–4).

Cited by 7 publications

References 45 publications

Development of a novel ReaxFF reactive potential for organochloride molecules

Development of a novel ReaxFF reactive potential for organochloride molecules

Specific-Ion Effects Unveil a Route for Modulating Oxidatively Triggered Acid Systems for Reservoir Applications

A ReaxFF Potential for Modeling Organic Matter Degradation with Oxybromine Oxidants

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