Purely-long-range bound states of He(2s3S)+(2s ^3S)+He(2p3P)(2p ^3P)

We predict the presence and positions of purely-long-range bound states of $^4$He$(2s ^3S)+{}^4$He$(2p ^3P)$ near the $2s ^3S_1+2p ^3P_{0,1}$ atomic limits. The results of the full multichannel and approximate models are compared, and we assess the sensitivity of the bound states to atomic parameters characterizing the potentials. Photoassociation to these purely-long-range molecular bound states may improve the knowledge of the scattering length associated with the collisions of two ultracold spin-polarized $^4$He$(2s ^3S)$ atoms, which is important for studies of Bose-Einstein condensates.Comment: 16 pages, 5 figure

An extensively validated C/H/O/N chemical network for hot exoplanet disequilibrium chemistry

Context: The reliability of one-dimensional disequilibrium chemistry models in hot exoplanet atmospheres depends on the chemical network used. To develop robust networks, we can rely on combustion studies that provide C/H/O/N chemical networks validated by vast amount of experimental data generated by the extensive research that has been done on hydrocarbon combustion and NOx formation in the last decades. // Aims: We aimed to build a new and updated C0–C2 chemical network to study the C/H/O/N disequilibrium chemistry of warm and hot exoplanet atmospheres that relies on extensively validated and recent state-of-the-art combustion networks. The reliability range of this network was aimed for conditions between 500–2500 K and 100–10−6 bar, with cautious extrapolation at lower temperature values. // Methods: We compared the predictions of seven networks over a large set of experiments, covering a wide range of conditions (pressures, temperatures, and initial compositions). To examine the consequences of this new chemical network on exoplanets atmospheric studies, we generated abundances profiles for GJ 436 b, GJ 1214 b, HD 189733 b, and HD 209458 b, using the 1D kinetic model FRECKLL and calculated the corresponding transmission spectra using TauREx 3.1. These spectra and abundance profiles have been compared with results obtained with our previous chemical network. // Results: Our new kinetic network is composed of 145 species and 1313 reactions mostly reversible. This network proves to be more accurate than our previous one for the tested experimental conditions. The nitrogen chemistry update is found to be very impactful on the abundance profiles, particularly for HCN, with differences up to four orders of magnitude. The CO2 profiles are also significantly affected, with important repercussions on the transmission spectrum of GJ 436 b. // Conclusions: These effects highlight the importance of using extensively validated chemical networks to gain confidence in our models predictions. As shown with CH2NH, the coupling between carbon and nitrogen chemistry combined with radicals produced by photolysis can have huge effects impacting the transmission spectra. This should be kept in mind when adding new elements like sulfur, as only adding a sub-mechanism neglects these coupling effects

Kinetics of the hydrogen abstraction ·C2H5 + alkane → C2H6 + alkyl reaction class: an application of the reaction class transition state theory

This paper presents an application of the reaction class transition state theory (RC-TST) to predict thermal rate constants for hydrogen abstraction reactions at alkane by the C2H5 radical on-the-fly. The linear energy relationship (LER), developed for acyclic alkanes, was also proven to hold for cyclic alkanes. We have derived all RCTST parameters from rate constants of 19 representative reactions, coupling with LER and the barrier height grouping (BHG) approach. Both the RC-TST/LER, where only reaction energy is needed, and the RC-TST/BHG, where no other information is needed, can predict rate constants for any reaction in this reaction class with satisfactory accuracy for combustion modeling. Our analysis indicates that less than 50% systematic errors on the average exist in the predicted rate constants using either the RC-TST/LER or RC-TST/BHG method, while in comparison with explicit rate calculations, the differences are within a factor of 2 on the average. The results also show that the RC-TST method is not sensitive to the choice of density functional theory used

Kinetics of 1,6-hydrogen migration in alkyl radical reaction class

The kinetics of the 1,6-intramolecular hydrogen migration in the alkyl radical reaction class has been studied using the reaction class transition state theory (RC-TST) combined with the linear energy relationship (LER) and the barrier height grouping (BHG) approach. The RC-TST/LER, where only reaction energy is needed, and RC-TST/BHG, where no other information is needed, are found to be promising methods for predicting rate constants for any reaction in the 1,6-intramolecular H migration in alkyl radicals reaction class. Direct comparison with available experimental data indicates that the RC-TST/LER, where only reaction energy is needed, can predict rate constants for any reaction in this reaction class with satisfactory accuracy

Intramolecular effects on the kinetics of unimolecular reactions of β-HOROO˙ and HOQ˙OOH radicals

Intramolecular effects involved in the unimolecular decomposition of oxygenated radicals formed during the low temperature combustion of alcohols and alkenes were investigated and kinetic correlations were proposed.</p

Theoretical study of the pyrolysis of β-1,4-xylan: a detailed investigation on unimolecular concerted reactions

A theoretical study of the thermal decomposition of β-1,4-xylan, a model polymer of hemicelluloses, is proposed for the first time.</p

AN AUTOMATIC MERGING PYTHON CODE FOR LARGE MECHANISM: EXAMPLE OF A TRF-IB MECHANISM

International audienceTIRAMISU, an automatic merging python code, was developed to generate and compare several kinetic models of combustion of toluene, n-heptane, isooctane, blended with isobutanol (toluene reference fuel-isobutanol, TRF-iB), based on detailed mechanisms from the literature. This code consists of a reading and cleaning step, followed by an automatic translation step and a merging and writing final step. Two different fusion tasks are presented: the full fusion of two mechanisms, a TRF and a model for alkyl aromatics (hereafter ALLNL), and the extraction of 3 different isobutanol sub-mechanisms and their integration into ALLNL