Barrierless reactions between two closed-shell molecules. II. Dynamics of F2 + CH3SSCH3 reaction.
A second example of a barrierless reaction between two closed-shell molecules is reported. The reaction F(2)+CH(3)SSCH(3) has been investigated with crossed molecular beam experiments and ab initio calculations. Compared with previous results of the F(2)+CH(3)SCH(3) reaction [J. Chem. Phys. 127, 101101 (2007); J. Chem. Phys. 128, 104317 (2008)], a new product channel leading to CH(3)SF+CH(3)SF is observed to be predominant in the title reaction, whereas the anticipated HF+C(2)H(5)S(2)F channel is not found. In addition, the F+C(2)H(6)S(2)F product channel, the analog to the F+C(2)H(6)SF channel in the F(2)+CH(3)SCH(3) reaction, opens up at collision energies higher than 4.3 kcal/mol. Angular and translational energy distributions of the products are reported and collision energy dependences of the reaction cross section and product branching ratio are shown. The reaction barrier is found to be negligible (<<1 kcal/mol). Multireference ab initio calculations suggest a reaction mechanism involving a short-lived intermediate which can be formed without activation energy.
Shao
Hua-Chieh
HC
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan.
Xie
Tingxian
T
Lu
Yu-Ju
YJ
Chang
Chih-Hsuan
CH
Pan
Jun-Wei
JW
Lin
Jim J
JJ