Potential Energy Surface For Reaction Research Articles

Multi-Level Protocol for Mechanistic Reaction Studies Using Semi-Local Fitted Potential Energy Surfaces

In this work, we propose a multi-level protocol for routine theoretical studies of chemical reaction mechanisms. The initial reaction paths of our investigated systems are sampled using the Nudged Elastic Band (NEB) method driven by a cheap electronic structure method. Forces recalculated at the more accurate electronic structure theory for a set of points on the path are fitted with a machine learning technique (in our case symmetric gradient domain machine learning or sGDML) to produce a semi-local reactive potential energy surface (PES), embracing reactants, products and transition state (TS) regions. This approach has been successfully applied to a unimolecular (Bergman cyclization of enediyne) and a bimolecular (SN2 substitution) reaction. In particular, we demonstrate that with only 50 to 150 energy-force evaluations with the accurate reference methods (here complete-active-space self-consistent field, CASSCF, and coupled-cluster singles and doubles, CCSD) it is possible to construct a semi-local PES giving qualitative agreement for stationary-point geometries, intrinsic reaction coordinates and barriers. Furthermore, we find a qualitative agreement in vibrational frequencies and reaction rate coefficients. The key aspect of the method’s performance is its multi-level nature, which not only saves computational effort but also allows extracting meaningful information along the reaction path, characterized by zero gradients in all but one direction. Agnostic to the nature of the TS and computationally economic, the protocol can be readily automated and routinely used for mechanistic reaction studies.

Study of the Potential Energy Surface of Reactions in a System Containing I-Propyl and N-Propyl Radicals

Study of the Potential Energy Surface of Reactions in a System Containing I-Propyl and N-Propyl Radicals

New Full-Dimensional Reactive Potential Energy Surface for the H4 System.

As the most abundant molecule in the universe, collisions involving H2 have important implications in astrochemistry. Collisions between hydrogen molecules also represent a prototype for assessing various dynamic methods for understanding fundamental few-body processes. In this work, we develop a new and highly accurate full-dimensional potential energy surface (PES) covering all reactive channels of the H2 + H2 system, which extends our previously reported H2 + H2 nonreactive PES [J. Chem. Theory Comput., 2021, 17, 6747] by adding 39,538 additional ab initio points calculated at the MRCI/AV5Z level in the reactive channels. The global PES is represented with high fidelity (RMSE = 0.6 meV for a total of 79,000 points) by a permutation invariant polynomial neural network (PIP-NN) and is suitable for studying collision-induced dissociation, single-exchange, as well as four-center exchange reactions. Preliminary quasi-classical trajectory studies on the new PIP-NN PES reveal strong vibrational enhancement of all reaction channels.

Solvent Polarity Effects on the Mechanochemistry of Spiropyran Ring Opening.

The spiropyran mechanophore (SP) is employed as a reporter of molecular tension in a wide range of polymer matrices, but the influence of surrounding environment on the force-coupled kinetics of its ring opening has not been quantified. Here, we report single-molecule force spectroscopy studies of SP ring opening in five solvents that span normalized Reichardt solvent polarity factors (ETN) of 0.1-0.59. Individual multimechanophore polymers were activated under increasing tension at constant 300 nm s-1 displacement in an atomic force microscope. The extension results in a plateau in the force-extension curve, whose midpoint occurs at a transition force f* that corresponds to the force required to increase the rate constant of SP activation to approximately 30 s-1. More polar solvents lead to mechanochemical reactions that are easier to trigger; f* decreases across the series of solvents, from a high of 415 ± 13 pN in toluene to a low of 234 ± 9 pN in n-butanol. The trend in mechanochemical reactivity is consistent with the developing zwitterionic character on going from SP to the ring-opened merocyanine product. The force dependence of the rate constant (Δx‡) was calculated for all solvent cases and found to increase with ETN, which is interpreted to reflect a shift in the transition state to a later and more productlike position. The inferred shift in the transition state position is consistent with a double-well (two-step) reaction potential energy surface, in which the second step is rate determining, and the intermediate is more polar than the product.

On the General Mechanism for the Gas-phase Reaction of Methanimine with a Radical Species in the Interstellar Medium: Some Failures and an Important Success

Abstract The gas-phase reactions of methanimine (CH2NH) with small radicals, such as CN, CP, CCH, and OH, have been extensively studied theoretically in the literature, and the presence of a common, general reaction mechanism has been postulated. Since methanimine is considered the main precursor of complex imines in the interstellar medium (ISM), the present study extends the investigation of its reaction with other small radicals that have already been detected in the ISM. These are SiN, SH, NO, NS, HCO, HCS, and C3N. The corresponding products are easily formulated on the basis of the aforementioned general mechanism, and to understand whether they can be formed in the ISM, a preliminary thermochemical study has been carried out. The only exothermic addition reaction is that occurring between CH2NH and the C3N radical. This reaction has been further investigated in order to accurately characterize its reactive potential energy surface, which has then been employed in ab initio transition state theory calculations to derive global rate coefficients. The products of the CH2NH + C3N reaction are new potential interstellar species, namely, the Z and E isomers of HNCHCCCN and CH2NCCCN. For the first time, their structural characterization has been reported. In addition, this work investigates the possibility of H-abstraction processes for each radical species considered, and re-examines the CH2NH + CP reaction to derive the corresponding rate constants, that were still missing in the literature.

Theoretical study on iso‐pentanol oxidation chemistry: Fuel radical isomerization and decomposition kinetics and mechanism development

AbstractThis study undertakes a detailed theoretical investigation into the iso‐pentanol radical isomerization and decomposition kinetics and the mechanism development of the iso‐pentanol oxidation. The CCSD(T)/CBS//M08‐HX/6‐311+G(2df,2p) method was adopted to calculate the reaction potential energy surface. The reaction rate coefficients were calculated by variational transition state theory (VTST) with multistructural torsional (MS‐T) partition function and small curvature tunneling (SCT) correction. Moreover, the pressure‐dependent rate coefficients were determined using the system‐specific quantum Rice‐Ramsperger‐Kassel theory (SS‐QRRK). The variational and tunneling effects were discussed, and the dominant reaction channels were identified. It reveals that the isomerization reactions play a significant role at low temperatures, while the decomposition reactions dominate the high‐temperature regime. Notably, the quantitative rate expressions for iso‐pentanol radical decomposition reactions were also obtained. Furthermore, a new kinetic model incorporating the calculated rate coefficients was constructed, exhibiting satisfactory prediction performance on ignition delay times and improved predictive accuracy of species mole fractions. This work provides accurate rate data of isomerization and decomposition kinetics and contributes to a more comprehensive understanding of the iso‐pentanol oxidation mechanism.

Benchmark ab initio characterization of the multi-channel Cl + CH3X [X = F, Cl, Br, I] reactive potential energy surfaces.

We determine benchmark geometries and relative energies for the stationary points of the Cl + CH3X [X = F, Cl, Br, I] reactions. We consider four possible reaction pathways: hydrogen abstraction, hydrogen substitution, halogen abstraction, and halogen substitution, where the substitution processes can proceed via either Walden inversion or front-side attack. We perform geometry optimizations and obtain harmonic vibrational frequencies at the explicitly-correlated UCCSD(T)-F12b/aug-cc-pVTZ level of theory, followed by UCCSD(T)-F12b/aug-cc-pVQZ single-point computations to make finite-basis-set error negligible. To reach chemical (<1 kcal mol-1), or even subchemical (<0.5 kcal mol-1) accuracy, we include core-correlation, scalar relativistic, post-(T), spin-orbit-splitting and zero-point-energy contributions, as well, in the relative energies of all the stationary points. Our benchmark 0 K reaction enthalpies are compared to available experimental results and show good agreement. The stationary-point structures and energetics are interpreted in terms of Hammond's postulate and used to make predictions related to the dynamical behavior of these reactive systems.

Navigating the Potential Energy Surface of CdSe Magic-Sized Clusters: Synthesis and Interconversion of Atomically Precise Nanocrystal Polymorphs.

Magic-sized clusters (MSCs) are kinetically stable, atomically precise intermediates along the quantum dot (QD) reaction potential energy surface. Literature precedent establishes two classes of cadmium selenide MSCs with QD-like inorganic cores: one class is proposed to be cation-rich with a zincblende crystal structure, while the other is proposed to be stoichiometric with a "wurtzite-like" core. However, the wide range of synthetic protocols used to access MSCs has made direct comparisons of their structure and surface chemistry difficult. Furthermore, the physical and chemical relationships between MSC polymorphs are yet to be established. Here, we demonstrate that both cation-rich and stoichiometric CdSe MSCs can be synthesized from identical reagents and can be interconverted through the addition of either excess cadmium or selenium precursor. The structural and compositional differences between these two polymorphs are contrasted using a combination of 1H NMR spectroscopy, X-ray diffraction (XRD), pair distribution function (PDF) analysis, inductively coupled plasma optical emission spectroscopy, and UV-vis transient absorption spectroscopy. The subsequent polymorph interconversion reactions are monitored by UV-vis absorption spectroscopy, with evidence for an altered cluster atomic structure observed by powder XRD and PDF analysis. This work helps to simplify the complex picture of the CdSe nanocrystal landscape and provides a method to explore structure-property relationships in colloidal semiconductors through atomically precise synthesis.

Single-atom catalysis in space: Computational exploration of Fischer–Tropsch reactions in astrophysical environments

Context. Gas-phase chemistry at extreme conditions (low densities and temperatures) is difficult, so the presence of interstellar grains is especially important for the synthesis of molecules that cannot form in the gas phase. Interstellar grains are advocated to enhance the encounter rate of the reactive species on their surfaces and to dissipate the energy excess of largely exothermic reactions, but less is known of their role as chemical catalysts that provide low activation energy pathways with enhanced reaction rates. Different materials with catalytic properties are present in interstellar environments, like refractory grains containing space-abundant d-block transition metals. Aims. In this work we report for first time mechanistic insights on the Fischer–Tropsch methanol (CH3OH) synthesis under astrophysical conditions using single-atom Fe-containing silica surfaces as interstellar heterogeneous catalysts. Methods. Quantum chemical calculations considering extended periodic surfaces were carried out in order to search for the stationary points and transitions states to finally construct the reaction potential energy surfaces. Binding energy and kinetic calculations based on the Rice–Ramsperger–Kassel–Marcus (RRKM) scheme were also performed to evaluate the catalytical capacity of the grain and to allocate those reaction processes within the astrochemical framework. Results. Our mechanistic studies demonstrate that astrocatalysis is feasible in astrophysical environments. Thermodynamically the proposed process is largely exergonic, but kinetically it shows energy barriers that would need from an energy input in order to go through. Kinetic calculations also demonstrate the strong temperature dependency of the reaction process as tunnelling is not relevant in the involved energetic barriers. The present results can explain the presence of CH3OH in diverse regions where current models fail to reproduce its observational quantity. Conclusions. The evidence of astrocatalysis opens a completely new spectrum of synthetic routes triggering chemical evolution in space. From the mechanistic point of view the formation of methanol catalysed by a single atom of Fe0 is feasible; however, its dependency on the temperature makes the energetics a key issue in this scenario.

The conversion mechanism of syngas CO and H2 under Au and Au-CCo-doping catalysts

The relative stability, reaction potential energy surface, NBO charge analysis and kinetic properties of Au, Au-C co-doping catalysts in CO and H2 syngas catalytic reactions were studied by density functional theory calculation. The calculation results indicate that the reaction energy barrier and reaction rate showed a consistent pattern of change. NBO charge analysis indicates the feasibility of the catalytic reaction of syngas. We also calculated the rate constant which indicates that the rate constant has a positive temperature dependence. Our calculations show that the reaction is an exothermic reaction catalyzed by Au and Au-C co-doping.

A Gaussian Process Based Δ-Machine Learning Approach to Reactive Potential Energy Surfaces.

The Gaussian process (GP) is an efficient nonparametric machine learning (ML) method. A distinct advantage of the GP is its ability to provide an estimate of statistical uncertainties. This is particularly useful in constructing high-dimensional potential energy surfaces (PESs) from ab initio data as it offers an optimal way to add new geometries to reduce the overall error. In this work, GP is employed in the context of Δ-machine learning (Δ-ML), in which a correction PES to an inaccurate low-level PES is constructed using a small number of high-level ab initio calculations. This new method is tested in three prototypical reactive systems, namely, the H + H2 → H + H2, OH + H2 → H2O + H, and H + CH4 → H2 + CH3 reactions. The results show that the GP-based Δ-ML approach is more efficient than its direct application in constructing high-level PESs. We also compare the new method to a previously proposed neural-network-based Δ-ML approach [Liu and Li J. Phys. Chem. Lett. 2022, 13, 4729-4738]. The results indicate that the two Δ-ML methods have comparable efficiencies in constructing accurate PESs.

Study on the methane dehydrogenation reaction catalyzed by triangular transition metal: a theoretical research

The relative stability, reaction potential energy surface, naturally bonded orbit (NBO) charge analysis, and kinetic properties of triangular transition metal catalysts in methane dehydrogenation reaction were studied by density functional theory calculation. The calculation results indicate that the process of triangular metal adsorption of methane is physical adsorption, and the main products of the reaction are hydrogen and carbon-based materials. This reaction is a multicomponent reaction. NBO charge analysis indicates the feasibility of the catalytic reaction of methane dehydrogenation. We also calculated the rate constant which indicates that the rate constant has a positive temperature dependence. Our calculations show that the reaction is an exothermic reaction catalyzed by triangular transition metal catalyzer.

Fragment-based models for dissociation of strong acids in water: Electrostatic embedding minimizes the dependence on the fragmentation schemes.

Fragmentation methods such as MIM (Molecules-in-Molecules) provide a route to accurately model large systems and have been successful in predicting their structures, energies, and spectroscopic properties. However, their use is often limited to systems at equilibrium due to the inherent complications in the choice of fragments in systems away from equilibrium. Furthermore, the presence of charges resulting from any heterolytic bond breaking may increase the fragmentation error. We have previously suggested EE-MIM (Electrostatically Embedded Molecules-In-Molecules) as a method to mitigate the errors resulting from the missing long-range interactions in molecular clusters in equilibrium. Here, we show that the same method can be applied to improve the performance of MIM to solve the longstanding problem of dependency of the fragmentation energy error on the choice of the fragmentation scheme. We chose four widely used acid dissociation reactions (HCl, HClO4, HNO3, and H2SO4) as test cases due to their importance in chemical processes and complex reaction potential energy surfaces. Electrostatic embedding improves the performance at both one and two-layer MIM as shown by lower EE-MIM1 and EE-MIM2 errors. The EE-MIM errors are also demonstrated to be less dependent on the choice of the fragmentation scheme by analyzing the variation in fragmentation energy at the points with more than one possible fragmentation scheme (points where the fragmentation scheme changes). EE-MIM2 with M06-2X as the low-level resulted in a variation of less than 1 kcal/mol for all the cases and 1 kJ/mol for all but three cases, rendering our method fragmentation scheme-independent for acid dissociation processes.

Spin-orbit charge transfer from guanine and 9-methylguanine radical cations to nitric oxide radicals and the induced triplet-to-singlet intersystem crossing.

Nitric oxide (●NO) participates in many biological activities, including enhancing DNA radiosensitivity in ionizing radiation-based radiotherapy. To help understand the radiosensitization of ●NO, we report reaction dynamics between ●NO and the radical cations of guanine (a 9HG●+ conformer) and 9-methylguanine (9MG●+). On the basis of the formation of 9HG●+ and 9MG●+ in the gas phase and the collisions of the radical cations with ●NO in a guided-ion beam mass spectrometer, the charge transfer reactions of 9HG●+ and 9MG●+ with ●NO were examined. For both reactions, the kinetic energy-dependent product ion cross sections revealed a threshold energy that is 0.24 (or 0.37) eV above the 0K product 9HG (or 9MG) + NO+ asymptote. To interrogate this abnormal threshold behavior, the reaction potential energy surface for [9MG + NO]+ was mapped out at closed-shell singlet, open-shell singlet, and triplet states using density functional and coupled cluster theories. The results showed that the charge transfer reaction requires the interaction of a triplet-state surface originating from a reactant-like precursor complex 3[9MG●+(↑)⋅(↑)●NO] with a closed-shell singlet-state surface evolving from a charge-transferred complex 1[9MG⋅NO+]. During the reaction, an electron is transferred from π∗(NO) to perpendicular π∗(9MG), which introduces a change in orbital angular momentum. The latter offsets the change in electron spin angular momentum and facilitates intersystem crossing. The reaction threshold in excess of the 0K thermochemistry and the low charge-transfer efficiency are rationalized by the vibrational excitation in the product ion NO+ and the kinetic shift arising from a long-lived triplet intermediate.

Mechanistic investigation of hydrogen generation from water and magnesium catalyst reaction: Advanced reactive molecular dynamics simulation

Magnesium is an effective catalyst for producing hydrogen through thermochemical water splitting. However, the slow reaction between Mg and water prevents this catalyst from being commercially useful. In this study, reactive MD simulations with accurate force fields and reactive potential energy surfaces are used to comprehend the slow-kinetics of the Mg-water reaction. At room temperature, water is split when it interacts with Mg nanoparticles and forms a Mg–H bond. Furthermore, at temperatures above 1200 K, Mg–H bonds begin to dissociate, resulting in the generation of hydrogen radicals from the Mg–H bond. The percentage of H–H bonds is almost zero until the reaction pathway reaches temperature 2000K, after which H radicals combine to form hydrogen gas. The analysis of temperature dependent data reveals that oxygen and hydrogen atoms combine with Mg elements to form massive stable linear and branched chains, resulting in slow Mg-water reaction kinetics for hydrogen production. Therefore, current studies utilizing reactive molecular dynamics can provide a means of improving the kinetics of the Mg-water reaction.

Ab Initio and Statistical Rate Theory Exploration of the CH (X2Π) + OCS Gas-Phase Reaction.

The first theoretical results regarding the gas-phase reaction mechanism and kinetics of the CH (X2Π) + OCS reaction are presented here. This reaction has a proposed importance in the removal of OCS in regions of the interstellar medium (ISM) and has the potential to form the recently observed HCS/HSC isomers, with both constitutional isomers having recently been observed in the L483 molecular cloud in a 40:1 ratio. Statistical rate theory simulations were performed on stationary points along the reaction potential energy surface (PES) obtained from ab initio calculations at the RO-CCSD(T)/aug-cc-pV(Q+d)Z//M06-2X-D3/aug-cc-pV(Q+d)Z level of theory over the temperature and total density range of 150-3000 K and 1011-1024 cm-3, respectively, using a Master Equation analysis. Exploration of the reaction potential energy surface revealed that all three pathways identified to create CS + HCO products required surmounting barriers of 16.5 kJ mol-1 or larger when CH approached the oxygen side of OCS, rendering this product formation negligible below 1000 K, and certainly under low-temperature ISM conditions. In contrast, when CH approaches the sulfur side of OCS, only submerged barriers are found along the reaction potential energy surface to create HCCO + S or CO + HCS, both of which are formed via a strongly bound OCC(H)S intermediate (-358.9 kJ mol-1). Conversion from HCS to HSC is possible via a barrier of 77.8 kJ mol-1, which is still -34.1 kJ mol-1 below the CH + OCS entrance channel. No direct route from CH + OCS to H + CO + CS was found from our ab initio calculations. Rate theory simulations suggest that the reaction has a strong negative temperature dependence, in accordance with the barrierless addition of CH to the sulfur side of OCS. Product branching fractions were also determined from MESMER simulations over the same temperature and total density range. The product branching fraction of CO + HCS reduces from 79% at 150 K to 0.0% at 800 K, while that of HCS dissociation to H + CS + CO increases from 22% at 150 K to 100% at 800 K. The finding of CO + HCS as the major product at the low temperatures relevant to the ISM, instead of H + CS + CO, is in opposition to the current supposition used in the KIDA database and should be adapted in astrochemical models as another source of the HCS isomer.

Objective molecular dynamics investigation of dissociation and recombination kinetics in high-temperature nitrogen

In this study, we propose the use of the novel approach of objective molecular dynamics (OMD) simulating far-from-equilibrium gas dynamics problems with chemical reactions. The OMD method has an exact relation to models in continuum mechanics and can be used to improve those models. We provide a detailed molecular dynamics investigation of chemically reacting nitrogen gas in a space-homogeneous adiabatic reactor. The analysis is based on a first-principles derived reactive ReaxFF potential energy surface, which captures the relevant processes of rovibrational relaxation, dissociation, and exchange as well as recombination in a gas evolving under non-equilibrium conditions. We examine the evolution of the internal mode population distribution of all the molecules as well as the rovibrational probability distribution of the pre-collision dissociating and post-collision recombined N2 molecules to investigate the microscopic selectivity of various reactive processes. Subsequently, we make comparisons with results obtained by means of an alternative modeling approach called direct molecular simulation. The current work illustrates the application of the method of OMD to study the compression and expansion kinetics of dissociation-recombination nitrogen mixture relevant to normal shock wave and nozzle expansion.

Multifidelity Neural Network Formulations for Prediction of Reactive Molecular Potential Energy Surfaces

This paper focuses on the development of multifidelity modeling approaches using neural network surrogates, where training data arising from multiple model forms and resolutions are integrated to predict high-fidelity response quantities of interest at lower cost. We focus on the context of quantum chemistry and the integration of information from multiple levels of theory. Important foundations include the use of symmetry function-based atomic energy vector constructions as feature vectors for representing structures across families of molecules and single-fidelity neural network training capabilities that learn the relationships needed to map feature vectors to potential energy predictions. These foundations are embedded within several multifidelity topologies that decompose the high-fidelity mapping into model-based components, including sequential formulations that admit a general nonlinear mapping across fidelities and discrepancy-based formulations that presume an additive decomposition. Methodologies are first explored and demonstrated on a pair of simple analytical test problems and then deployed for potential energy prediction for C5H5 using B2PLYP-D3/6-311++G(d,p) for high-fidelity simulation data and Hartree-Fock 6-31G for low-fidelity data. For the common case of limited access to high-fidelity data, our computational results demonstrate that multifidelity neural network potential energy surface constructions achieve roughly an order of magnitude improvement, either in terms of test error reduction for equivalent total simulation cost or reduction in total cost for equivalent error.

Collision of C2 with NH and deuterated analogs in the interstellar medium. Scattering calculations

ABSTRACT Shephard’s interpolation potential energy surface and isotopic substitution were used to understand the mechanisms of chemical reactions; the NH + C2 reaction potential energy surface was constructed in this research and evaluated using ab-initio calculations. Classical trajectory simulations were used to calculate the reaction probability and cross-section. In addition, the rate constant by the nonlinear least-squares fitting was calculated. These were determined as a function of cross-section. In non-reactive trajectories for inelastic collisions, the scattering angle was estimated. The effects of the impact parameter and the relative velocity of particles on the reaction probability, transmitted energy, and dispersion angle were investigated. In addition, Isotopic substitution in the NH radical was evaluated for the effect of the mass of the target and incident particles on the cross-section, reaction probability, dispersion angle, and reaction rate. To calculate the kinetic isotope effect, the influence of the mass of colliding molecules on the observable properties was studied. Deuterated imidogen reacted faster than hydrogenated imidogen. These observations provided valuable insights into the details of the mechanisms, possible reactions of ND and NH + C2 , and deuterium fractionation.

High-temperature mid-IR absorption and reaction kinetics of 2-methyl-1,3-dioxolane: An experimental and theoretical study

This work reports the mid-IR spectroscopy and reaction kinetics of 2-methyl-1,3-dioxolane (2M13DO). We carried out spectroscopic measurements to deduce temperature-dependent absorption cross-sections of 2M13DO over a broad wavelength range of 8.4–10.5 μm (950–1190 cm−1). For these measurements, we employed a rapidly tuning MIRcat-QT™ laser that can be operated either at a fixed wavelength or scanned mode over wide wavelength regions. By operating the laser at a fixed wavelength, we monitored the decay of 2M13DO behind reflected shock waves over T5 = 1050–1400 K and P5 = 0.7 and 2.6 bar. Our measured concentration time-histories of 2M13DO allowed us to directly extract the overall rate coefficients for the unimolecular decomposition of 2M13DO using the first-order rate law. We did not observe any pressure dependence in the measured rate coefficients, indicating that the reaction is close to the high-pressure limit. By employing the W1U composite method, we explored the important pyrolysis reaction pathways of 2M13DO in the reactive potential energy surface. Three important reaction channels, namely, 2M13DO → CH2CHOCH2CH2OH (IM1), 2M13DO → 2CH3CHO (P3), 2M13DO → CH3 + 1,3-dioxolan-2-yl (P4) were identified. Below 700 K, IM1 forming channel is dominant, whereas CH3CHO formation is dominant under our experimental conditions. Above 1500 K, the radical forming channel (CH3+P4) takes over other channels. At higher temperatures, the contribution of the radical forming channel continually increases, accounting for ∼ 99% at 2000 K. We used the stochastic RRKM-ME model to predict the pressure and temperature dependence of the rate coefficients, k(T, P), and time-resolved species profiles. Our theory showed excellent agreement with the measured rate coefficients. These are the first direct determination of the rate coefficients of the unimolecular decomposition of 2M13DO.