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Exploring the spin–orbit reactivity in the simplest chlorine atom reaction
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23.The direction of the product being detected (H atom) is referred to the c.m. direction of the reactant from which the H atom originates.
24.The absolute energetic uncertainty was estimated to be 0.2 kcal/mol, mostly arising from the exact location of the origin of the c.m. frame. As a consequence, the peak of the product HCl rotational quantum state distribution could be off by one unit.
25.Even taking into account experimental error bars and allowing for some small negative values in the map as a consecutive estimate, Cl* is still three to four times more reactive than Cl. The more precise determination of the relative reactivity for Cl* is currently planned, which will involve a totally different approach. Nevertheless, we are confident that the present finding of will stand the test of time.
26.To our knowledge, the only previous reaction that violates the conventional spin–orbit propensity is the isoelectronic ion–molecule reaction of by Tanaka, Durup, Kato, and Koyano in J. Chem. Phys. 74, 5561 (1981). It was found that the excited is more reactive than the ground atom by a factor of ∼1.4. To interpret this intriguing observation, a mechanism invoked the crossings and transitions of the and surfaces with the PES was proposed. This charge transfer mechanism is unique to ion–molecule or a neutral reaction via the harpooning mechanism, and is not applicable to the present case.
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