The reaction involving atomic carbon in its first electronically excited state 1D and methane has been investigated in crossed molecular beam experiments at a collision energy of 25.3 kJ mol-1. Electronic structure calculations of the underlying potential energy surface (PES) and Rice–Ramsperger–Kassel–Marcus (RRKM) estimates of rates and branching ratios have been performed to assist the interpretation of the experimental results. The reaction proceeds via insertion of C(1D) into one of the C-H bonds of methane leading to the formation of the intermediate HCCH3 (methylcarbene or ethylidene), which either decomposes directly into the products C2H3 + H or C2H2 + H2 or isomerizes to the more stable ethylene, which in turn dissociates into C2H3 + H or H2CC + H2. The experimental results indicate that the H-displacement and H2-elimination channels are of equal importance and that for both channels the reaction mechanism is controlled by the presence of a bound intermediate, the lifetime of which is comparable to its rotational period. On the contrary, RRKM estimates predict a very short lifetime for the insertion intermediate and the dominance of the H-displacement channel. It is concluded that the reaction C(1D)+CH4 cannot be described statistically and a dynamical treatment is necessary to understand its mechanism. Possibly, nonadiabatic effects are responsible for the discrepancies, as triplet and singlet PES of methylcarbene cross each other and intersystem crossing is possible. Similarities with the photodissociation of ethylene and with the related reactions N(2D) + CH4, O(1D) + CH4 and S(1D) + CH4 are also commented on.

Combined crossed beam and theoretical studies of the C(1D)+CH4 reaction

SKOUTERIS, Dimitrios;
2013

Abstract

The reaction involving atomic carbon in its first electronically excited state 1D and methane has been investigated in crossed molecular beam experiments at a collision energy of 25.3 kJ mol-1. Electronic structure calculations of the underlying potential energy surface (PES) and Rice–Ramsperger–Kassel–Marcus (RRKM) estimates of rates and branching ratios have been performed to assist the interpretation of the experimental results. The reaction proceeds via insertion of C(1D) into one of the C-H bonds of methane leading to the formation of the intermediate HCCH3 (methylcarbene or ethylidene), which either decomposes directly into the products C2H3 + H or C2H2 + H2 or isomerizes to the more stable ethylene, which in turn dissociates into C2H3 + H or H2CC + H2. The experimental results indicate that the H-displacement and H2-elimination channels are of equal importance and that for both channels the reaction mechanism is controlled by the presence of a bound intermediate, the lifetime of which is comparable to its rotational period. On the contrary, RRKM estimates predict a very short lifetime for the insertion intermediate and the dominance of the H-displacement channel. It is concluded that the reaction C(1D)+CH4 cannot be described statistically and a dynamical treatment is necessary to understand its mechanism. Possibly, nonadiabatic effects are responsible for the discrepancies, as triplet and singlet PES of methylcarbene cross each other and intersystem crossing is possible. Similarities with the photodissociation of ethylene and with the related reactions N(2D) + CH4, O(1D) + CH4 and S(1D) + CH4 are also commented on.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11384/14842
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