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Crossed beam reactions of methylidyne [CH(X2Π)] with D2-acetylene [C2D2(X1Σg+)] and of D1-methylidyne [CD(X2Π)] with acetylene [C2H2(X1Σg+)]
Ralf I. Kaiser,Xibin Gu,Fangtong Zhang,Pavlo Maksyutenko
Physical Chemistry Chemical Physics Pub Date : 11/22/2011 00:00:00 , DOI:10.1039/C1CP22635E
Abstract

The crossed molecular beam reactions of ground state methylidyne, CH(X2Π), with D2-acetylene, C2D2(X1Σg+), and of D1-methylidyne, CD(X2Π), with acetylene, C2H2(X1Σg+), were conducted under single collision conditions at a collision energy of 17 kJ mol−1. Four competing reaction channels were identified in each system following atomic ‘hydrogen’ (H/D) and molecular ‘hydrogen’ (H2/D2/HD) losses. The reaction dynamics were found to be indirect via complex formation and were initiated by two barrierless-addition pathways of methylidyne/D1-methylidyne to one and to both carbon atoms of the D2-acetylene/acetylene reactant yielding HCCDCD/DCCHCH and c-C3D2H/c-C3H2D collision complexes, respectively. The latter decomposed via atomic hydrogen/deuterium ejection to form the thermodynamically most stable cyclopropenylidene species (c-C3H2, c-C3D2, c-C3DH). On the other hand, the HCCDCD/DCCHCH adducts underwent hydrogen/deuterium shifts to form the propargyl radicals (HDCCCD, D2CCCH; HDCCCH, H2CCCD) followed by molecular ‘hydrogen’ losses within the rotational plane of the decomposing complex yielding l-C3H/l-C3D. Quantitatively, our crossed beam studies suggest a dominating atomic compared to molecular ‘hydrogen’ loss with fractions of 81 ± 23% vs. 19 ± 10% for the CD/C2H2 and 87 ± 30% vs. 13 ± 4% for the CH/C2D2 systems. The role of these reactions in the formation of interstellar isomers of C3H2 and C3H is also discussed.

Graphical abstract: Crossed beam reactions of methylidyne [CH(X2Π)] with D2-acetylene [C2D2(X1Σg+)] and of D1-methylidyne [CD(X2Π)] with acetylene [C2H2(X1Σg+)]
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