Observation and interpretation of a time-delayed mechanism in the hydrogen exchange reaction

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Abstract
Extensive theoretical1,2,3,4,5,6,7,8,9,10,11,12,13 and experimental2,13,14,15,16,17,18,19,20,21,22 studies have shown the hydrogen exchange reaction H + H2 → H2 + H to occur predominantly through a ‘direct recoil’ mechanism: the H–H bonds break and form concertedly while the system passes straight over a collinear transition state, with recoil from the collision causing the H2 product molecules to scatter backward. Theoretical predictions agree well with experimental observations of this scattering process15,16,17,18,19,20,22. Indirect exchange mechanisms involving H3 intermediates have been suggested to occur as well8,9,10,11,12,13, but these are difficult to test because bimolecular reactions cannot be studied by the femtosecond spectroscopies23 used to monitor unimolecular reactions. Moreover, full quantum simulations of the time evolution of bimolecular reactions have not been performed. For the isotopic variant of the hydrogen exchange reaction, H + D2 → HD + D, forward scattering features21 observed in the product angular distribution have been attributed21,12 to possible scattering resonances associated with a quasibound collision complex. Here we extend these measurements to a wide range of collision energies and interpret the results using a full time-dependent quantum simulation of the reaction, thus showing that two different reaction mechanisms modulate the measured product angular distribution features. One of the mechanisms is direct and leads to backward scattering, the other is indirect and leads to forward scattering after a delay of about 25 femtoseconds.

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