title: A CASPT2 theoretical study of the kinetics of the 2-, 3-, and 4-methylbenzylperoxy radical isomerization.
abstract: The rate constants of the 2-, 3-, and 4-methylbenzylperoxy isomerization reactions have been computed using the elaborated CASPT2 method. Geometry optimizations and vibrational frequency calculations are performed with two methods (B3LYP and MPW1K) combined with the cc-pVDZ and 6-31+G(d,p) basis sets, respectively. Single-point energy calculations are performed at the CASPT2/ANO-L-VDZP//B3LYP/cc-pVDZ level of theory as recommended by Canneaux et al. (J. Phys. Chem. A 2008, 112, 6045). Canonical transition-state theory with a simple Wigner tunneling correction is used to predict the high-pressure limit rate constants as a function of temperature. They are given by the following relations for the 2-, 3-, and 4-methylbenzylperoxy (MBP) (1,3s) isomerizations and for the 2-methylbenzylperoxy (1,6p) isomerization, respectively: k(2-MBP(1,3s))(600-2000 K) (in s(-1)) = (3.33 x 10(10))T(0.79) exp((-142.6 in kJ mol(-1))/RT); k(3-MBP(1,3s))(600-2000 K) (in s(-1)) = (0.74 x 10(10))T(0.79) exp((-130.7 in kJ mol(-1))/RT); k(4-MBP(1,3s))(600-2000 K) (in s(-1)) = (1.12 x 10(10))T(0.79) exp((-133.6 in kJ mol(-1))/RT); k(2-MBP(1,6p))(600-2000 K) (in s(-1)) = (5.10 x 10(8))T(0.85) exp((-87.1 in kJ mol(-1))/RT). These parameters can be used in the thermokinetic models involving aromatic compounds at high pressure. In the case of the 2-methylbenzylperoxy radical, the (1,6p) H-atom transfer reaction is consistently the most important channel over the studied temperature range, and the (1,3s) H-atom transfer reaction is not energetically favored.
authors.affiliation: UMR CNRS 8522, FR CNRS 2416 Centre d'Etudes et de Recherche Lasers et Applications, Universite des Sciences et Technologies de Lille, Villeneuve d'Ascq, France. sebastien.canneaux@univ-lille1.fr
authors.forename: Sébastien
authors.initials: S
authors.lastname: Canneaux
authors.forename: Florent
authors.initials: F
authors.lastname: Louis
authors.forename: Marc
authors.initials: M
authors.lastname: Ribaucour
authors.forename: Abderrahman
authors.initials: A
authors.lastname: El Bakali
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Pauwels