title: Structural dynamics effects on the ultrafast chemical bond cleavage of a photodissociation reaction.
abstract: The correlation between chemical structure and dynamics has been explored in a series of molecules with increasing structural complexity in order to investigate its influence on bond cleavage reaction times in a photodissociation event. Femtosecond time-resolved velocity map imaging spectroscopy reveals specificity of the ultrafast carbon-iodine (C-I) bond breakage for a series of linear (unbranched) and branched alkyl iodides, due to the interplay between the pure reaction coordinate and the rest of the degrees of freedom associated with the molecular structure details. Full-dimension time-resolved dynamics calculations support the experimental evidence and provide insight into the structure-dynamics relationship to understand structural control on time-resolved reactivity.
authors.affiliation: Departamento de Química Física, Facultad de Ciencias Químicas (Unidad Asociada I+D+i al CSIC), Universidad Complutense de Madrid, 28040 Madrid, Spain. lbanares@ucm.es.
authors.forename: María E
authors.initials: ME
authors.lastname: Corrales
authors.forename: Vincent
authors.initials: V
authors.lastname: Loriot
authors.forename: Garikoitz
authors.initials: G
authors.lastname: Balerdi
authors.forename: Jesús
authors.initials: J
authors.lastname: González-Vázquez
authors.forename: Rebeca
authors.initials: R
authors.lastname: de Nalda
authors.forename: Luis
authors.initials: L
authors.lastname: Bañares
authors.forename: Ahmed H
authors.initials: AH
authors.lastname: Zewail
mesh_terms: D006846:Hydrocarbons, Halogenated / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D055668:Photochemical Processes; D013997:Time Factors
chemical_list: D006846:Hydrocarbons, Halogenated