First-Principles Computed Rate Constant for the O + O 2 Isotopic Exchange Reaction Now Matches Experiment

2018

We show, by performing exact time-independent quantum molecular scattering calculations, that the quality of the ground electronic state global potential energy surface appears to be of utmost importance in accurately obtaining even as strongly averaged quantities as kinetic rate constants. The oxygen isotope exchange reaction, 18O + 32O2, motivated by the understanding of a complex long-standing problem of isotopic ozone anomalies in the stratosphere and laboratory experiments, is explored in this context. The thermal rate constant for this key reaction is now in quantitative agreement with all experimental data available to date. A significant recent progress at the frontier of three rese…

MeCaSDa and ECaSDa: Methane and ethene calculated spectroscopic databases for the virtual atomic and molecular data centre

2013

Abstract Two spectroscopic relational databases, denoted MeCaSDa and ECaSDa, have been implemented for methane and ethene, and included in VAMDC (Virtual Atomic and Molecular Data Centre, http://portal.vamdc.eu/vamdc_portal/home.seam ). These databases collect calculated spectroscopic data from the accurate analyses previously performed for the electronic ground state of methane, ethene, and some of their isotopologues: 12CH4, 13CH4, and 12C2H4. Both infrared absorption and Raman scattering lines are included. The polyad structures are reported and the transitions are precisely described by their energy, their intensity and the full description of the lower and upper states involved in the …

Extension of the MIRS computer package for the modeling of molecular spectra : from effective to full ab initio ro-vibrational hamiltonians in irredu…

2012

The MIRS software for the modeling of ro-vibrational spectra of polyatomic molecules was considerably extended and improved. The original version (Nikitin, et al. JQSRT, 2003, pp. 239--249) was especially designed for separate or simultaneous treatments of complex band systems of polyatomic molecules. It was set up in the frame of effective polyad models by using algorithms based on advanced group theory algebra to take full account of symmetry properties. It has been successfully used for predictions and data fitting (positions and intensities) of numerous spectra of symmetric and spherical top molecules within the vibration extrapolation scheme. The new version offers more advanced possib…

EXO-PLANETARY HIGH-TEMPERATURE HYDROCARBONS BY EMISSION AND ABSORPTION SPECTROSCOPY (e-PYTHEAS PROJECT)

2019

International audience; e-PYTHEAS is a multidisciplinary project which combines theoretical and experimental work with exoplanet modelling applications. It sits on the frontier between molecular physics, theoretical chemistry and astrophysics. It aims at enhancing our understanding of the radiative properties of hot gaseous media to allow for improved analysis and interpretation of the large mass of data available on the thousands of exoplanets and exoplanetary systems known to date. Our approach is to use theoretical research validated by laboratory experiments and to then inject it into models of the atmospheres of the giant gaseous planets in the solar system and other planetary systems.…

Quantum mechanical study of the 16O + 18O18O → 16O18O + 18O exchange reaction: Integral cross sections and rate constants

2018

The isotopic exchange reaction, 16O + 18O18O → 16O18O + 18O, involving excited ozone, O3*, as intermediate complex, was investigated by means of a time independent quantum mechanical approach using the TKTHS potential energy surface (PES) [V. G. Tyuterev et al., J. Chem. Phys. 139, 134307 (2013)] of ozone. State-to-state integral cross sections were calculated for collision energies lower than 0.4 eV. Then specific and thermal rate constants were computed between 10 K and 350 K using these cross sections. The full quantum thermal rate constant is found to be in better agreement with the most recent experimental data than with previous studies where other O3 PESs were employed, confirming th…

Methane line parameters in HITRAN

2003

Abstract Two editions of the methane line parameters (line positions, intensities and broadening coefficients) available from HITRAN in 2000 and 2001 are described. In both versions, the spectral interval covered was the same (from 0.01 to 6184.5 cm −1 ), but the database increased from 48,033 transitions in 2000 to 211,465 lines in 2001 because weaker transitions of 12 CH 4 and new bands of 13 CH 4 and CH3D were included. The newer list became available in 2001 in the “Update” section of HITRAN. The sources of information are described, and the prospects for future improvements are discussed.

Applications of a new set of methane line parameters to the modeling of Titan's spectrum in the 1.58 μm window

2012

International audience; In this paper we apply a recently released set of methane line parameters (Wang et al., 2011) to the modeling of Titan spectra in the 1.58 mu m window at both low and high spectral resolution. We first compare the methane absorption based on this new set of methane data to that calculated from the methane absorption coefficients derived in situ from DISR/Huygens (Tomasko et al., 2008a; Karkoschka and Tomasko, 2010) and from the band models of Irwin et al. (2006) and Karkoschka and Tomasko (2010). The Irwin et al. (2006) band model clearly underestimates the absorption in the window at temperature-pressure conditions representative of Titan's troposphere, while the Ka…

Simulations of Titan Observations in the 1.58 Micron Transparency Window with High-Resolution, Low Temperature CRDS Spectra

2010

Virtual Atomic and Molecular Data Center

2010

(special issue HighRus2009). VAMDC; International audience

Le Cycle du Méthane sur Titan

2009

Applications of a New Methane Linelist to the Modeling of Titan's Spectrum in the 1.58 Micron Window

2011

International audience

First Applications of New Methane Linelists to the Modelling of Titan's Spectrum in the 1.58 and 1.28 Micron Windows

2010

Study of ν1/ν3 interacting bands of silane : analysis of infrared and Raman spectra

1990

International audience; The ν1/ν3 interacting bands of natural silane have been studied by Fourier transform spectroscopy and stimulated Raman spectroscopy, respectively, in the regions 2040–2320 and 2180–2187 cm−1. These data combined with available microwave observations have been analyzed using a reduced effective Hamiltonian developed through the fifth order for 28SiH4 and through the fourth order for 29SiH4 and 30SiH4. The observed infrared and Raman transitions have been very well reproduced with a standard deviation of about 0.0004 cm−1 for 28SiH4. Some anomalies in the Hamiltonian expansion have been found, but they did not perturb the analysis.

Calculs variationnels globaux et approche algébrique pour les états ro-vibrationnels très excités des molécules diatomiques

2008

VAMDC: Databases of Calculated Spectral Lines of Ethylene and Methane

2011

Application of new methane linelists to Cassini and Earth-based data of Titan

2011

International audience