47 research outputs found
Purely-long-range bound states of HeHe
We predict the presence and positions of purely-long-range bound states of
HeHe near the 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 He atoms, which is important for studies of
Bose-Einstein condensates.Comment: 16 pages, 5 figure
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
An extensively validated C/H/O/N chemical network for hot exoplanet disequilibrium chemistry
This is the author accepted manuscript We aimed to build a new and updated C0-C2 chemical network to study the CHON
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. 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. Our new kinetic network is
composed of 174 species and 1293 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 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. 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.Agence Nationale de la RechercheCentre National d’Études Spatiales (CNES)CNRS/INS
Thermal cracking of n -butylbenzene at high pressure: Experimental study and kinetic modelling
International audienceHighlights Pyrolysis of n-butylbenzene at 70 MPa and from 583 K to 623 K was performed in sealed gold tubes. The main products are toluene, ethylbenzene, iso-heptyl-and iso-butylbenzene, CH4 and C2H6. A detailed kinetic model was constructed and validated over the entire experimental range of conversion (0.7-62%). Thermochemical and kinetic parameters of key decomposition routes were computed using theoretical calculations