Skip to Main content Skip to Navigation
Theses

Ré-investigation de la photo-dynamique du salicylidène aniline par spectroscopie d'absorption transitoire femtoseconde et analyse multivariée des données

Abstract : This work is interested in the photo-dynamics of photochromism of salicylidene aniline (SA) in solution aiming at proposing a general mechanism. As the photochormism of SA involves an ultrafast intramolecular proton transfer, the experimental study consisted mainly in femtosecond transient absorption spectroscopy at different excitation wavelengths. The observation of ultrafast photo-induced processes by pump-probe spectroscopy techniques requires measuring and taking into account the instrumental response function. Indeed some physical effects affect the structure of spectrokinetic data, some distortions may be observed, as well as convolution limiting the time resolution of the measurement. The first part of this work dealt with an adaptation of multivariate chemometric tools, to take into account these specificities. The proposed approach implements a dedicated kinetic constraint into the multivariate curve resolution-alternating least squares method (MCR-ALS). The methodological developments were validated on simulated data and then being applied to the spectroscopic study of SA. The main points are: 1) the intramolecular proton transfer, which was estimated at 60 fs, 2) the existence of a competitive rotation mechanism which was characterized, 3) the excitation wavelength dependence of quantum yields values. Finally, a complete characterization of the photo-induced processes of SA, i.e. the reaction rates and the spectra of all the transient species, was provided and discussed.
Document type :
Theses
Complete list of metadata

https://tel.archives-ouvertes.fr/tel-00689167
Contributor : Hervé Vezin Connect in order to contact the contributor
Submitted on : Thursday, April 19, 2012 - 2:08:00 PM
Last modification on : Wednesday, March 23, 2022 - 3:50:15 PM
Long-term archiving on: : Friday, July 20, 2012 - 2:30:50 AM

Identifiers

  • HAL Id : tel-00689167, version 1

Collections

Citation

Nicolas Mouton. Ré-investigation de la photo-dynamique du salicylidène aniline par spectroscopie d'absorption transitoire femtoseconde et analyse multivariée des données. Chimie théorique et/ou physique. Université des Sciences et Technologie de Lille - Lille I, 2011. Français. ⟨tel-00689167⟩

Share

Metrics

Record views

127

Files downloads

274