title: Absolute rate coefficients over extended temperature ranges and mechanisms of the CF(X(2)Pi) reactions with F(2), Cl(2) and O(2).
abstract: The absolute rate coefficients of the reactions of the carbyne-radical CF(X(2)Pi, nu = 0) with O(2), F(2) and Cl(2) have been measured over extended temperature ranges, using pulsed-laser photodissociation-laser-induced fluorescence (PLP-LIF) techniques. The CF(X(2)Pi) radicals were generated by KrF excimer laser 2-photon photolysis of CF(2)Br(2) at 248 nm and the real-time exponential decays of CF(X(2)Pi, nu = 0) at varying coreactant concentrations, in large excess, were monitored by LIF (A(2)Sigma(+), nu' = 1 <-- X(2)Pi, nu'' = 0 transition). The experimental bimolecular rate coefficients of the CF(X(2)Pi) reactions with F(2) and Cl(2) can be described by simple Arrhenius expressions: k(F2)(295-408 K) = (1.5 +/- 0.2) x 10(-11) exp[-(370 +/- 40)K/T] cm(3) molecule(-1) s(-1); and k(Cl2)(295-392 K) = (6.1 +/- 2.1) x 10(-12) exp[+(280 +/- 120)K/T]. The k(F2)(T) and k(Cl2)(T) results can be rationalized in terms of direct halogen-atom abstraction reactions in which the radical character of CF dominates; a quantum chemical CBS-Q//BHandHLYP/6-311G(d,p) study confirms that the ground state reactants CF(X(2)Pi) + F(2)(X(1)Sigma) connect directly with the ground-state products CF(2)(X(1)A(1)) + F((2)P) via a nearly barrierless F-atom abstraction route. The rate coefficient of CF(X(2)Pi) + O(2) can be represented by a two-term Arrhenius expression: k(O2)(258-780 K) = 1.1 x 10(-11) exp(-850 K/T) + 2.3 x 10(-13) exp(500 K/T), with a standard deviation of 5%. The first term dominates at higher temperatures T and the second at lower T where a negative temperature dependence is observed (<290 K). Quantum chemical computations at the CBS-QB3 and CCSD(T)/aug-cc-pVDZ levels of theory show that the k(O2)(T) behaviour is consistent with a change of the dominant rate-determining mechanism from a carbyne-type insertion into the O-O bond at high T to a radical-radical combination at low T.
authors.affiliation: Department of Chemistry, University of Leuven, Celestijnenlaan 200F, B-3001, Leuven, Belgium.
authors.forename: B
authors.initials: B
authors.lastname: Vetters
authors.forename: B
authors.initials: B
authors.lastname: Dils
authors.forename: T L
authors.initials: TL
authors.lastname: Nguyen
authors.forename: L
authors.initials: L
authors.lastname: Vereecken
authors.forename: S A
authors.initials: SA
authors.lastname: Carl
authors.forename: J
authors.initials: J
authors.lastname: Peeters