Low Reaction Barrier Research Articles

The Effect of N‐Defect and Axial Halogen Atom on Electrocatalytic Oxygen Reduction Reaction Activity of FeN4 Single‐Atom Catalysts: A Density Functional Theory Study

AbstractSingle atom catalysts had been widely used in oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). However, the relationship between local coordination environment and catalytic activity were unclear. In this work, the effect of N‐defect and axial halogen atoms on electrocatalytic OER/ORR activity of FeN4 catalysts were investigated by density functional theory calculations (DFT). When the overpotential was the only criterion, FeN3Br was the optimal candidates for OER, followed by FeN3F, FeN4I, FeN4Cl and FeN4Br; FeN4I, FeN4Br and FeN4Cl were also the promising candidates for ORR. FeN4I, FeN4Br and FeN4Cl may be excellent ORR catalysts in an acidic media because of the low overpotential and reaction barrier of kinetics rate limiting step. In summary, N‐defect and axial halogen atoms can effectively balance kinetics, thermodynamics and catalytic activity.

Enhancing silicon-nitride formation through ammonolysis of silanes with pseudo-halide substituents.

Considering the challenges in reactivity, potential contamination, and substrate selectivity, the ammonolysis of traditional halosilanes in silicon nitride (SiN) thin film processing motivates the exploration of alternative precursors. In this pioneering study, we employed density functional theory calculations at the M06-2X/6-311++G(3df,2p) level to comprehensively screen potential pseudo-halide substituents on silane compounds as substitutes for conventional halosilanes. Initially, we investigated the ammonolysis mechanism of halosilanes, exploring factors influencing activation barriers, with the aid of frontier molecular orbital and charge density analyses. Subsequently, a systematic screening of silane substituents from group 14 to group 16 was conducted to identify pseudo-halides with low reaction barriers. Additionally, we examined the inductive effects on pseudohalide substituents. Using cluster models to represent the silicon surface validates the realistic prediction of ammonolysis barriers with a simplified model. Our findings indicate that pseudo-halide substituents from group 16, particularly those with electron-withdrawing groups, present as practical alternatives to traditional halosilanes in SiN thin film processing, including applications such as low-temperature atomic layer deposition (ALD) techniques.

Multilevel quantum mechanical calculations show the role of promoter molecules in the dehydration of methanol to dimethyl ether in H-ZSM-5.

Methyl carboxylate esters promote the formation of dimethyl ether (DME) from the dehydration of methanol in H-ZSM-5 zeolite. We employ a multilevel quantum method to explore the possible associative and dissociative mechanisms in the presence, and absence, of six methyl ester promoters. This hybrid method combines density functional theory, with dispersion corrections (DFT-D3), for the full periodic system, with second-order Møller-Plesset perturbation theory (MP2) for small clusters representing the reaction site, and coupled cluster with single, double, and perturbative triple substitution (CCSD(T)) for the reacting molecules. The calculated adsorption enthalpy of methanol, and reaction enthalpies of the dehydration of methanol to DME within H-ZSM-5, agree with experiment to within chemical accuracy (∼4 kJ mol-1). For the promoters, a reaction pathway via an associative mechanism gives lower overall reaction enthalpies and barriers compared to the reaction with methanol only. Each stage of this mechanism is explored and related to experimental data. We provide evidence that suggests the promoter's adsorption to the Brønsted acid site is the most important factor dictating its efficiency.

Spin-polarized p-block antimony/bismuth single-atom catalysts on defect-free rutile TiO2(110) substrate for highly efficient CO oxidation.

Developing high-loading spin-polarized p-block-element-based single-atom catalysts (p-SACs) upon defect-free substrates for various chemical reactions wherein spin selection matters is generally considered a formidable challenge because of the difficulty of creating high densities of underpinning stable defects and the delocalized electronic features of p-block elements. Here our first-principles calculations establish that the defect-free rutile TiO2(110) wide-bandgap semiconducting anchoring support can stabilize and localize the wavefunctions of p-block metal elements (Sb and Bi) via strong ionic bonding, forming spin-polarized p-SACs. Cooperated by the underlying d-block Ti atoms via a delicate spin donation-back-donation mechanism, the p-block single-atom reactive center Sb(Bi) exhibits excellent catalysis for spin-triplet O2 activation and CO oxidation in alignment with Wigner's spin selection rule, with a low rate-limiting reaction barrier of ∼0.6 eV. This work is crucial in establishing high-loading reactive centers of high-performance p-SACs for various important physical processes and chemical reactions, especially wherein the spin degree of freedom matters, i.e., spin catalysis.

(Invited) First Principles Examination of Multiple Criteria of Organic Solvent Oxidative Stability in Batteries

Oxidative instability of the liquid electrolyte at or near battery cathode oxide surfaces has significant detrimental effects on batteries. Organic solvent molecules are often the fuel and precurors of such degradation processes, releasing electrons and protons that react with cathode oxides and electrolyte anions. These reactions contribute to cathode electrolyte interphase (CEI) film formation, transition metal ion dissolution, and phase transformation of the surface regions of the cathode. Here we apply Density Functional Theory calculations to examine four criteria of oxidative stability (oxidation potential, hydrogen removal energies, and initial reactivity on two types of oxide facets) using four different solvent/additive molecules (ethylene carbonate, fluoroethylene carbonate, 1,3-dioxolane, and dimethyl ether). The ranking of molecular stability differs with each criterion. Surprisingly, the all-oxygen terminated basal planes of layered oxides exhibit lower reaction barriers than spinel surface facets with exposed transition metal cations, especially for ether solvents; the calculations also suggest basal planes contribute to the dissolution of transition metal ions. The structure-degradation relation complexity underscores the challenge of understanding the function of the CEI, but also offers a guide to future degradation-mitigation strategies including facet-engineering. Our predictions and models help establish a framework for future studies relevant to high voltage conditions.Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the document do not necessarily represent the views of the U.S. Department of Energy or the United States Government.

Screening seven-electron boron-centered radicals for dinitrogen activation.

The activation of dinitrogen is significant as nitrogen-containing compounds play an important role in industries. However, the inert NN triple bond caused by its large HOMO-LUMO gap (10.8 eV) and high bond dissociation energy (945 kJ mol-1 ) renders its activation under mild conditions particularly challenging. Recent progress shows that a few main group species can mimic transition metal complexes to activate dinitrogen. Here, we demonstrate that a series of seven-electron (7e) boron-centered radical can be used to activate N2 via density functional theory calculations. It is found that boron-centered radicals containing amine ligand perform best on the thermodynamics of dinitrogen activation. In addition, when electron-donating groups are introduced at the boron atom, these radicals can be used to activate N2 with low reaction barriers. Further analysis suggests that the electron transfer from the boron atom to the π* orbitals of dinitrogen is essential for its activation. Our findings suggest great potential of 7e boron radicals in the field of dinitrogen activation.

Controlling C–C coupling reactivity through pore shape engineering of B-doped graphyne family

Graphyne is an interesting carbon allotrope characterized by sp-sp2 hybridized carbon bonds, which allow for structure variability. Though there are studies evaluating the electrical and mechanical properties of various structures, studies utilizing its structural variety toward catalyst applications are minor. In electrocatalytic CO2 reduction reactions (CRR), producing valuable C2+ products, such as C2H4 or C2H5OH, under mild conditions is still challenging. The bottleneck has been assigned to the carbon-carbon (C–C) coupling reaction, such as 2*CO → *OCCO. In this reaction, one requires strong binding to the catalyst to enhance neighboring CO concentration, but at the same time, one needs to have low C–C coupling barriers making the OC-CO bond. Following our previous study, which showed B-doped γ-graphyne can be a catalyst for ethanol production, we conducted theoretical investigations on a range of B-doped graphyne families using density functional theory. Out of the 15 different structures studied, four, 4,12,2-, sR-, γ-, and 6,6,12-graphynes, show promising potential for CRR. B-doped 4,12,2-graphyne, with small square and rectangular pores, had a very low C–C coupling barrier of 0.34 eV with strong 2*CO adsorption (−2.5 eV). Furthermore, our research revealed a correlation between the heat of reaction (2*CO → *OCCO) and the average pore area around the acetylenic linker reaction site. Smaller pores give a favorable orientation of two CO molecules, resulting in low reaction barriers.

Unraveling the Unimolecular Ion Chemistry of Protonated Isoprene and Prenol.

The atmospheric chemistries of isoprene and prenol have been studied extensively; however, much of that research has focused on neutral or radical chemistry. Recent studies have demonstrated that under acidic conditions, isoprene and prenol can become protonated in the atmosphere, and we have explored the unimolecular chemistry of protonated isoprene and prenol with tandem mass spectrometry (using a triple-quadrupole mass spectrometer) and density functional theory. The collision-induced dissociation of protonated isoprene revealed two product ion channels: the neutral losses of C2H4 and H2, the former dominating over the latter. Protonated prenol dissociates by four product ion channels: the neutral losses of water, formaldehyde, methanol, and propene, with the former two being minor channels and the latter two being major channels. Density functional theory supplemented with CBS-QB3 single-point calculations revealed the underlying mechanisms to explain the breakdown behavior. The two competing channels from protonated isoprene could easily be rationalized due to the relative energy difference between key transition states along the reaction coordinates. However, in the case of protonated prenol, it was revealed that the minor products observed in the breakdown of protonated prenol had significantly lower reaction barriers when compared to the major products, an apparent contradiction. This could be rationalized if the initial ion population entering the collision cell is comproed of several isomeric species on the minimum energy reaction pathway, species populated by collisional excitation in the ion source region.

Identifying the active site and structure–activity relationship in propane dehydrogenation over Ga2O3/ZrO2 catalysts

ZrO2-based catalysts have attracted extensive attention in propane dehydrogenation (PDH) owing to their environmental compatibility, low costs, and superior catalytic performance. However, the structure–activity relationship and mechanistic analysis of Ga2O3/ZrO2 in PDH are rarely studied where GaOx either acts as an active site or a promoter. Here, Ga2O3/ZrO2 catalysts with different Ga/Zr ratios were synthesized by the impregnation technique, and the structure–activity relationship was revealed by combining complementary in/ex-situ characterization methods with catalytic tests. It is found the rate of propene formation first increases linearly and then reaches a plateau with the increase of Ga2O3 loading, such activity-loading dependence is related to the evolution of Ga2O3 species varying from monodisperse to single-layer and then multilayer states. Activation energy and C3H8-TPSR results suggest the formation of a new active site with high intrinsic activity over Ga2O3/ZrO2. Furthermore, the molecular level reaction mechanism of Ga2O3/ZrO2 in PDH was studied by DFT calculations, which pointed out the active site structure was GaⅡ–O3cⅡ site exhibiting enhanced activation ability toward C–H bond and lower reaction barrier compared with bare ZrO2. This work is expected to offer new insights into understanding the structure–activity relationships over ZrO2-based catalysts for PDH reaction.

Experimental investigation and molecular simulation on the chemical bonding between laser-treated titanium alloy amorphous surface and epoxy adhesive

ABSTRACT Laser surface modification is employed to enhance the interfacial bonding performance of metal-adhesive structures, and chemical bonding plays a crucial role in achieving strong interfacial adhesion. Understanding the mechanism of interfacial chemical bonding between laser-treated metal surface and adhesive at the molecular/atomic scale is key to further optimizing the interfacial bonding performance. In this study, the morphology and chemical composition of laser-induced amorphous titanium oxide on titanium alloy surfaces, as well as its enhanced effect on interfacial bonding performance, were characterized using scanning electron microscopy, energy dispersive spectroscopy, and single lap-shear testing.Through X – ray photoelectron spectroscopy analysis, experimental evidence is provided for the formation of Ti-O-C chemical bonds between the amorphous titanium oxide and adhesive. Transmission electron microscopy observations and molecular dynamics simulations reveal that the strong non-bonding intereactions between amorphous titanium oxide and adhesive enables the adhesive molecules to fully infiltrate the amorphous titanium oxide, providing more sites for chemical bond formation. Density functional theory calculations demonstrate that Ti-O-C chemical bonds tend to form between the dissociated hydroxyl group of the adhesive and titanium oxide, facilitated by a relatively low reaction barrier. This chemical bonding promote the formation of a strong bonding structure at the adhesive interface.

Orientation-dependent etching of silicon by fluorine molecules: A quantum chemistry computational study

Anisotropic etching is a widely used process in semiconductor manufacturing, in particular, for micro- and nanoscale texturing of silicon surfaces for black silicon production. The typical process of plasma-assisted etching uses energetic ions to remove materials in the vertical direction, creating anisotropic etch profiles. Plasmaless anisotropic etching, considered here, is a less common process that does not use ions and plasma. The anisotropy is caused by the unequal etching rates of different crystal planes; the etching process, thus, proceeds in a preferred direction. In this paper, we have performed quantum chemistry modeling of gas-surface reactions involved in the etching of silicon surfaces by molecular fluorine. The results confirm that orientation-dependent etch rates are the reason for anisotropy. The modeling of F2 dissociative chemisorption on F-terminated silicon surfaces shows that Si–Si bond breaking is slow for the Si(111) surface, while it is fast for Si(100) and Si(110) surfaces. Both Si(100) and Si(110) surfaces incorporate a larger number of fluorine atoms resulting in Si–Si bonds having a larger amount of positive charge, which lowers the reaction barrier of F2 dissociative chemisorption, yielding a higher etch rate for Si(100) and Si(110) surfaces compared to Si(111) surfaces. Molecular dynamics modeling of the same reactions has shown that the chosen reactive bond order potential does not accurately reproduce the lower reaction barriers for F2 dissociative chemisorption on Si(100) and Si(100) surfaces. Thus, reparameterization is necessary to model the anisotropic etching process that occurs at lower temperatures.

Anode‐Less All‐Solid‐State Batteries Operating at Room Temperature and Low Pressure

AbstractAnode‐less all‐solid‐state batteries (ASSBs) are being targeted for next‐generation electric mobility owing to their superior energy density and safety as well as the affordability of their materials. However, because of the anode‐less configuration, it is nontrivial to simultaneously operate the cell at room temperature and low pressure as a result of the sluggish reaction kinetics of lithium (de)plating and the formation of interfacial voids. This study overcomes these intrinsic challenges of anode‐less ASSBs by introducing a dual thin film consisting of a magnesium upper layer with a Ti3C2Tx MXene buffer layer underneath. The Mg layer enables reversible Li plating and stripping at room temperature by reacting with Li via a (de)alloying reaction with a low reaction barrier. The MXene buffer layer maintains the electrolyte‐electrode interface by inhibiting the formation of voids even at low pressure of 2 MPa owing to the high ductility of MXene. This study highlights the importance of a combined chemical and mechanical approach when designing anode‐less electrodes for practical adaptation for anode‐less ASSBs.

Allosteric control of olefin isomerization kinetics via remote metal binding and its mechanochemical analysis

Allosteric control of reaction thermodynamics is well understood, but the mechanisms by which changes in local geometries of receptor sites lower activation reaction barriers in electronically uncoupled, remote reaction moieties remain relatively unexplored. Here we report a molecular scaffold in which the rate of thermal E-to-Z isomerization of an alkene increases by a factor of as much as 104 in response to fast binding of a metal ion to a remote receptor site. A mechanochemical model of the olefin coupled to a compressive harmonic spring reproduces the observed acceleration quantitatively, adding the studied isomerization to the very few reactions demonstrated to be sensitive to extrinsic compressive force. The work validates experimentally the generalization of mechanochemical kinetics to compressive loads and demonstrates that the formalism of force-coupled reactivity offers a productive framework for the quantitative analysis of the molecular basis of allosteric control of reaction kinetics. Important differences in the effects of compressive vs. tensile force on the kinetic stabilities of molecules are discussed.

Deep reaction network exploration of glucose pyrolysis

Resolving the reaction networks associated with biomass pyrolysis is central to understanding product selectivity and aiding catalyst design to produce more valuable products. However, even the pyrolysis network of relatively simple [Formula: see text]-D-glucose remains unresolved due to its significant complexity in terms of the depth of the network and the number of major products. Here, a transition-state-guided reaction exploration has been performed that provides complete pathways to most significant experimental pyrolysis products of [Formula: see text]-D-glucose. The resulting reaction network involves over 31,000 reactions and transition states computed at the semiempirical quantum chemistry level and approximately 7,000 kinetically relevant reactions and transition states characterized with density function theory, comprising the largest reaction network reported for biomass pyrolysis. The exploration was conducted using graph-based rules to explore the reactivities of intermediates and an adaption of the Dijkstra algorithm to identify kinetically relevant intermediates. This simple exploration policy surprisingly (re)identified pathways to most major experimental pyrolysis products, many intermediates proposed by previous computational studies, and also identified new low-barrier reaction mechanisms that resolve outstanding discrepancies between reaction pathways and yields in isotope labeling experiments. This network also provides explanatory pathways for the high yield of hydroxymethylfurfural and the reaction pathway that contributes most to the formation of hydroxyacetaldehyde during glucose pyrolysis. Due to the limited domain knowledge required to generate this network, this approach should also be transferable to other complex reaction network prediction problems in biomass pyrolysis.

Highly effective and recyclable ZnCo2O4@NF for peroxymonosulfate activation towards ciprofloxacin degradation: Dual reaction sites and enhanced electron transfer mechanisms

The nano/micro-sized catalysts for peroxymonosulfate (PMS) activation often undergo agglomeration, leading to inevitable loss of active sits and reduced catalytic efficiency. Herein, monolith nickel foam (NF) supported ZnCo2O4 nanosheets were constructed, achieving almost complete removal of ciprofloxacin (CIP) within 15 min. ZnCo2O4@NF exhibits prominent stability in microstructure and exposed active sites, resulting in high reusability. The unique Zn-O-Co structure and “conducting bridge” of NF could accelerate the electron transfer from ZnCo2O4 to PMS and the following O-O bond cleavage. This facilitates Co2+/Co3+ redox cycle for continuous SO4•− generation and endows ZnCo2O4@NF with low reaction barrier. The surface hydroxyl groups and the inner-sphere complexation between PMS and catalyst play significant role in the formation of reactive oxygen species (ROS). Furthermore, the quenching test confirmed the dominant role of SO4•− and auxiliary role of •OH/1O2 in ZnCo2O4@NF/PMS system. The reaction sites in CIP molecule easily attacked by ROS were determined, and the possible radical/non-radical degradation pathways of CIP were proposed. This work further unveiled the mechanism of the covalency and electronic configuration in ZnCo2O4@NF. The distinct advantages of the macroscopic catalyst including outstanding catalytic ability and high structural stability provide great possibility for broad industrial application.

Selective hydrogenation of crotonaldehyde over Ir/TiO2 catalysts: Unraveling the metal-support interface related reaction mechanism

For the supported catalysts for the selective hydrogenation of α, β - unsaturated aldehyde with H2, tailoring of metal - support interfacial effect to improve reaction performance is a significant but challenging subject. In this work, we regulated both the size regimes of the Ir deposits (single atom, nanocluster and nanoparticle) and the crystal plane of anatase TiO2 (TiO2(101), TiO2(100) and TiO2(001)) so as to alter the Ir-TiOx interfacial properties, in order to unravel reaction mechanism of selective hydrogenation of crotonaldehyde over the Ir/TiO2 catalysts. Both the activity and selectivity to crotyl alcohol increased as the Ir size grew from single atom to nanoparticle, ascribed to high Ir0 content, high concentration of surface defects and prominent H-spillover effect on the Ir nanoparticles. Moreover, the in situ Fourier transform infrared spectroscopy (FTIR) and density functional theory (DFT) calculations demonstrated that an end-on CO adsorption mode for crotonaldehyde molecule was favored at the Ir-TiOx interface particularly at high H coverage, which thus facilitated the hydrogenation of CO bond to form crotyl alcohol. Moreover, the highest reactivity of the Ir nanoparticles was evidenced by the lowest reaction barrier. These results explicitly demonstrate that larger metal nanoparticles and adsorption geometry of the reactant at the metal - support interface are vital for improved catalytic performance, which would shed light on the ingenious catalyst design.

Potential-Induced Synthesis and Structural Identification of Oxide-Derived Cu Electrocatalysts for Selective Nitrate Reduction to Ammonia

Developing effective electrocatalysts for nitrate reduction to ammonia is paramount for ammonia synthesis while addressing the water pollutant issue. Identifying the active structure and its correlation with catalytic behavior during the reaction process is essential and challenging for the rational design of advanced electrocatalysts. Herein, starting from Cu2O particles with controllable crystal facets, the electrochemically reconstituted Cu/Cu2O was fabricated as a suitable catalytic system, and the relationship between the chemical state of copper and product selectivity in the nitrate reduction reaction was studied. At −0.9 V versus reversible hydrogen electrode, the oxide-derived Cu0 (OD-Cu) cube achieved a high ammonia Faradaic efficiency of 93.9% and productivity of up to 219.8 μmol h–1 cm–2, surpassing those of most Cu-based catalysts. In situ Raman analysis, well-designed pulsed electrolysis experiments, and theoretical calculations showed that ammonia was preferentially produced on OD-Cu at high reduction potentials and the presence of the Cu/Cu2O interface favored nitrite formation at low reduction potentials. The high ammonia selectivity of the OD-Cu cube originated from the enhanced adsorption of nitrate and lower reaction barrier of the potential-determining step (*NH3 → NH3). This work presents an effective strategy to boost electrocatalysis and offers an insight into the real active phase and corresponding catalytic behavior of Cu-based electrocatalysts.

Regulating the C–H Bond Activation Pathway over ZrO2 via Doping Engineering for Propane Dehydrogenation

The efficient activation of the C–H bond in light alkanes and their catalyst design are significant for alkane-related catalytic processes in view of theoretical and practical aspects. Here, we report the C–H bond activation mechanism and structure–reactivity relationships of Ga-doped ZrO2 catalysts in propane dehydrogenation. Experimental and theoretical calculation results suggest that the introduction of Ga into the framework of ZrO2 alters the C–H bond activation pathway from a stepwise mechanism to a concerted mechanism involving simultaneous cleavage of two C–H bonds in propane, leading to a superior C–H bond activation ability and a lower reaction barrier than state-of-the-art metal oxide catalysts. In addition, a volcano-type dependence of the rate of propene formation on the Ga/Zr ratio is established due to a compromise of intrinsic activity and active site concentration. The strategy of metal incorporation into bulk metal oxide may provide an alternative solution to control the C–H bond activation pathway for efficient propene production.

Atomically Dispersed Fe–N4 and Ni–N4 Independent Sites Enable Bidirectional Sulfur Redox Electrocatalysis

Single-atom catalysts (SACs) with high atom utilization and outstanding catalytic selectivity are useful for improving battery performance. Herein, atomically dispersed Ni-N4 and Fe-N4 dual sites coanchored on porous hollow carbon nanocages (Ni-Fe-NC) are fabricated and deployed as the sulfur host for Li-S battery. The hollow and conductive carbon matrix promotes electron transfer and also accommodates volume fluctuation during cycling. Notably, the high d band center of Fe in Fe-N4 site demonstrates strong polysulfide affinity, leading to an accelerated sulfur reduction reaction. Meanwhile, Li2S on the Ni-N4 site delivers a metallic property with high S 2p electron density of states around the Femi energy level, enabling a low sulfur evolution reaction barrier. The dual catalytic effect on Ni-Fe-NC endows sulfur cathode high energy density, prolonged lifespan, and low polarization.

Determining Reaction Paths by Evaluating Kinetic Isotopic Effects with Density Functional Theory: Example of Methane Thermogenesis

This study demonstrates the determination of reaction pathways by evaluating the carbon kinetic isotopic effect and interpreting isotopic fractionations based on quantum chemical calculations. The reaction under investigation is methane thermogenesis from the decomposition of kerogen, which is a geochemical reaction under temperatures below 150 °C and lasts for tens of millions of years. Investigating its mechanism requires theoretical simulations because lab experiments at practical time-lengths require elevated temperatures, which introduce unwanted side reactions. Density functional theory and kinetic simulations were conducted on isotopic fractionations with the use of two possible pathways (free-radical versus carbonium), and the results were compared to field data sets. Different molecular sizes of kerogen were investigated to account for the hindrance of translation and rotation in modeling a reactant in the solid phase. Both pathways have low reaction barriers, implying that the reaction rates are limited by the concentration of active species (hydrated protons and free radicals). The results support the carbonium pathway and rule out the free-radical pathway as the 13CH4 from the latter would be 30‰ more depleted than the observed data. Additionally, simulations were conducted on hydrocarbon isotope fractionation of the carbonium pathway with consideration of hydrogen exchange between methane and water, successively reproducing the observed abundances of deuterium-containing isotopologues (13CH3D, 13CH3D, and 12CH2D2).