title: Kinetic and theoretical study of the reaction of Cl atoms with a series of linear thiols.
abstract: The reactions of Cl with a series of linear thiols: 1-propanethiol (k(1)), 1-butanethiol (k(2)), and 1-pentanethiol (k(3)) were investigated as a function of temperature (in the range of 268-379 K) and pressure (in the range of 50-200 Torr) by laser photolysis-resonance fluorescence. Only 1-propanethiol has previously been studied, but at 1 Torr of total pressure. The derived Arrhenius expressions obtained using our kinetic data were as follows: k(1)=(3.97+/-0.44)x10(-11) exp[(410+/-36)T], k(2)=(1.01+/-0.16)x10(-10) exp[(146+/-23)T], and k(3)=(1.28+/-0.10)x10(-10) exp[(129+/-25)T] (in units of cm(3) molecule(-1) s(-1)). Moreover, a theoretical insight into mechanisms of these reactions has also been pursued through ab initio Moller-Plesset second-order perturbation treatment calculations with 6-311G(**) basis set. Optimized geometries have been obtained for transition states and molecular complexes appearing along the different reaction pathways. Furthermore, molecular energies have been calculated at QCISD(T) level in order to get an estimation of the activation energies. Finally, the nature of the molecular complexes and transitions states is analyzed by using kinetic-potential and natural bond orbital total energy decomposition schemes.
authors.affiliation: Departamento de Quimica Fisica, Facultad de CC. Quimicas, Universidad de Castilla La Mancha, Avenida Camilo Jose Cela, s/n, 13071 Ciudad Real, Spain. agarzon@ujaen.es
authors.forename: Andrés
authors.initials: A
authors.lastname: Garzón
authors.forename: José
authors.initials: J
authors.lastname: Albaladejo
authors.forename: Alberto
authors.initials: A
authors.lastname: Notario
authors.forename: Tomás
authors.initials: T
authors.lastname: Peña-Ruiz
authors.forename: Manuel
authors.initials: M
authors.lastname: Fernández-Gómez
mesh_terms: D001272:Atmosphere / Q000737:chemistry; D002713:Chlorine / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D011312:Pressure; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013696:Temperature; D013816:Thermodynamics
chemical_list: D013438:Sulfhydryl Compounds; D002713:Chlorine