A framework for automatic discovery of chemically termolecular reactions

Barbet, Mark C.; McCullough, Kevin J.; Burke, Michael P.

doi:10.1016/j.proci.2018.05.002

Cited by 17 publications

(5 citation statements)

References 29 publications

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“…[20][21][22][23][24] Weakly bound radicals, which oen have Boltzmann distributions with signicant populations of energy states above the dissociation threshold, are recognized to be especially prone to such effects. 21,24,25 Furthermore, the complexes formed from association of two species can be formed with sufficiently high energy that they undergo rapid bimolecular reaction with a third species prior to their dissociation or stabilization, [26][27][28][29][30][31][32][33][34][35] yielding chemically termolecular reactions involving three reactants engaged in the bond transformations. 31 In both of such instances, signicant reactions across multiple potential energy surfaces occur on timescales that are comparable to internal energy relaxation, the manifestations of which continue to be the subject of considerable attention.…”

Section: Introductionmentioning

confidence: 99%

Dissociation-induced depletion of high-energy reactant molecules as a mechanism for pressure-dependent rate constants for bimolecular reactions

2022

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Section: Introductionmentioning

confidence: 99%

Dissociation-induced depletion of high-energy reactant molecules as a mechanism for pressure-dependent rate constants for bimolecular reactions

2022

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“…Since then, the importance of several other chemically termolecular reactions in combustion has been recognized. − As examples, Barbet et al identified a handful of chemically termolecular reactions of potential importance to combustion using a rapid, automated procedure for identifying and estimating rate constants of chemically termolecular reactions. Lei and Burke have since demonstrated that H + C 2 H 2 + O 2 one of the reactions identified in the screening study of Barbet et alimpacts predicted ignition delay times by an order of magnitude.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…Lei and Burke 10 have since demonstrated that H + C 2 H 2 + O 2  one of the reactions identified in the screening study of Barbet et al 9 impacts predicted ignition delay times by an order of magnitude. Cornell et al, 11 using the same screening procedure as Barbet et al, 9 identified yet more chemically termolecular reactions of potential importance to energetic materials combustion. Jasper et al 12 and Tao et al 13 have also found noticeable influences of H + CH 3 + X and H + OH + X (X = H, O, OH, O 2 ) on flame speeds.…”

Section: Introductionmentioning

confidence: 99%

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Understanding and Representing the Distinct Kinetics Induced by Reactive Collisions of Rovibrationally Excited Ephemeral Complexes across Reactive Collider Mole Fractions and Pressures

Lei

Burke

2020

J. Phys. Chem. A

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Rovibrationally excited ephemeral complexes AB**, formed from the association of two molecules A + B, are generally considered to undergo collisions only with an inert bath gas M that transfer energyinducing termolecular association reactions A + B (+M) → AB (+M). Recent studies have demonstrated that reactive collisions of AB** with a third molecule Cinducing chemically termolecular reactions A + B + C → productscan also be significant in combustion and planetary atmospheres. Previous studies on systems with reactive collisions have primarily focused on limited ranges of reactive collider mole fraction, X C , and pressure, P, specific to the chosen application. Yet, it remains to be established how such systems, and the rate constants of their emergent phenomenological reactions, behave over the wide X C and P ranges of potential interesta gap in the present understanding that has impeded the development of broadly applicable rate laws and general treatment of such systems in kinetic modeling. Here, we present results from master equation calculations for HO 2 ** formed from H + O 2 and its reactions with H to advance understanding and explore representations of systems with reactive colliders across wide ranges of X C and P. With regard to understanding, we demonstrate that reactive collisions can both (1) increase the overall rate of conversion of reactants to products and (2) alter the branching ratio among final products. With regard to representations in kinetic models, we find that rate constants of all emergent phenomenological reactionstermolecular association A + B (+M), chemically termolecular A + B + C, and bimolecular AB + Cexhibit a rich X C and P dependence. We also present analyses to explore the existence of a unique phenomenological representation (or lack thereof) and assess ways for the distinct effects of reactive collisions to be represented in kinetic models.

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“…A substantial fraction of the reactions that occur in combustion and planetary atmospheres proceed through rovibrationally excited intermediate complexes (i.e., “complex-forming” or “pressure-dependent” reactions). The fate of these complexes, and in turn the phenomelogical behavior that emerges from these reactions, is governed by the competition between reaction (unimolecular decomposition/isomerization − and even bimolecular reaction − ) and energy transfer via collisions with the surrounding bath gas.…”

Section: Introductionmentioning

confidence: 99%

Bath Gas Mixture Effects on Multichannel Reactions: Insights and Representations for Systems beyond Single-Channel Reactions

Lei

Burke

2018

J. Phys. Chem. A

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Nearly all studies of and available data for pressure-dependent reactions focus on pure bath gases. Of the comparatively fewer studies on bath gas mixtures, important to combustion and planetary atmospheres, nearly all focus on single-channel reactions. The present study explores, and seeks reliable representations of, bath gas mixture effects on multichannel reactions. Analytical and numerical solutions of the master equation here reveal several unique manifestations of mixture effects for multichannel reactions, including behavior completely opposite to trends observed for single-channel reactions. The most common way of evaluating mixture rate constants from data for pure components, the classic linear mixture rule, is found to yield errors exceeding a factor of ∼10. A new linear mixture rule based on the reduced pressure, instead of the absolute pressure, is found to be accurate within ∼30% for rate constants (and ∼50% for the branching ratio). A new nonlinear mixture rule that additionally incorporates analytically derived activity coefficients is found to be accurate within ∼10% for rate constants and branching ratios. These new mixture rules are therefore recommended for use in fundamental and applied chemical kinetics investigations of reacting mixtures, including reacting flow codes and experimental interpretations of third-body efficiencies.

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A framework for automatic discovery of chemically termolecular reactions

Cited by 17 publications

References 29 publications

Dissociation-induced depletion of high-energy reactant molecules as a mechanism for pressure-dependent rate constants for bimolecular reactions

Dissociation-induced depletion of high-energy reactant molecules as a mechanism for pressure-dependent rate constants for bimolecular reactions

Understanding and Representing the Distinct Kinetics Induced by Reactive Collisions of Rovibrationally Excited Ephemeral Complexes across Reactive Collider Mole Fractions and Pressures

Bath Gas Mixture Effects on Multichannel Reactions: Insights and Representations for Systems beyond Single-Channel Reactions

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