Transition State Spectroscopy of the Photoinduced Ca + CH3F Reaction. 2. Experimental and Ab Initio Studies of the Free Ca***FCH3 Complex - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Physical Chemistry A Année : 2006

Transition State Spectroscopy of the Photoinduced Ca + CH3F Reaction. 2. Experimental and Ab Initio Studies of the Free Ca***FCH3 Complex

Résumé

The Ca* + CH3F CaF* + CH3 reaction was photoinduced in 1:1 Ca***CH3F complexes formed in a supersonic expansion. The transition state of the reaction was explored by monitoring the electronically excited product, CaF, while scanning the laser that turns on the reaction. Moreover, the electronic structure of the Ca***FCH3 system was studied using ab initio methods by associating a pseudopotential description of the [Ca2+] and [F7+] cores, a core polarization operator on calcium, an extensive Gaussian basis and a treatment of the electronic problem at the CCSD(T) (ground state) and RSPT2 (excited states) level. In this contribution we present experimental results for the free complex and a comparison with the results of a previous experiment where the Ca***CH3F complexes are deposited at the surface of large argon clusters. The ab initio calculations allowed an interpretation of the experimental data in terms of two reaction mechanisms, one involving a partial charge transfer state, the other involving the excitation of the C-F stretch in the CH3F moiety prior to charge transfer.
Fichier principal
Vignette du fichier
jmm_06b_accepte.pdf (568.08 Ko) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)
Loading...

Dates et versions

hal-00126680 , version 1 (25-01-2007)

Identifiants

Citer

J.-M. Mestdagh, Fernand Spiegelman, Eric Gloaguen, M. Collier, F. Lepetit, et al.. Transition State Spectroscopy of the Photoinduced Ca + CH3F Reaction. 2. Experimental and Ab Initio Studies of the Free Ca***FCH3 Complex. Journal of Physical Chemistry A, 2006, 110, pp.7355-7363. ⟨10.1021/jp057483j⟩. ⟨hal-00126680⟩
122 Consultations
180 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More