Étude de la réduction de N2O par le mono- et dimère de titane à l'échelle moléculaire : Étude combinée expérimentale par la technique d'isolation en matrice de néon-FTIR et la chimie quantique

Abstract : From the spectroscopic study of the Ti, Ti2 + N2O reaction products trapped in rare gas matrices, we were able to identify three products for the reaction Ti + N2O (a simple van der Waals adduct, an end-on complex and a side-on molecule), and two for the 3Ti2 + N2O = 1[OTi2(η1 - NN)] or 1[OTiNTiN] reaction. We showed that the atomic titanium is unreactive with respect to N2O in its ground state, while the titanium dimer spontaneously reacts with N2O leading to the N-O bond scission and yielding to an intermediate adduct 1[OTi2(η1 - NN)]. A second bond breaking, the N-N bond cleavage, could be achieved by means of photochemistry, leading to the final product 1[OTiNTiN]. Over all the available functionals, none of them has been shown to systematically overshadow all the others. However, difficulties lie in choosing, from the plethora of density functionals, the one to apply. The selection of the functional to use depends on the problem at hand, i.e., on both the dispersion and static correlations. In this thesis, a strategy has been suggested in order to select the most adequate functional. It consists of a validation of calculation method for a given system by reproducing a set of reference data, obtained either by experiment or at the CCSD(T) or CASPT2 levels on the structural, energetic and vibrational properties.
Complete list of metadatas

Cited literature [156 references]  Display  Hide  Download

https://tel.archives-ouvertes.fr/tel-00945661
Contributor : Abes Star <>
Submitted on : Wednesday, February 12, 2014 - 4:32:54 PM
Last modification on : Friday, March 22, 2019 - 1:30:45 AM
Long-term archiving on : Tuesday, May 13, 2014 - 12:55:12 AM

File

these_archivage_NA_2860879.pdf
Version validated by the jury (STAR)

Identifiers

  • HAL Id : tel-00945661, version 1

Citation

Asma Marzouk Elmaalaoui. Étude de la réduction de N2O par le mono- et dimère de titane à l'échelle moléculaire : Étude combinée expérimentale par la technique d'isolation en matrice de néon-FTIR et la chimie quantique. Autre. Université Pierre et Marie Curie - Paris VI, 2014. Français. ⟨NNT : 2014PA066001⟩. ⟨tel-00945661⟩

Share

Metrics

Record views

486

Files downloads

1356