State-to-State Dynamics in Mode-Specific Reactions of Cl + CH3D(v1-I, v1-II, and v4 = 1; |10⟩): Loss of Memory or Not.

Several decades of the study of reaction dynamics culminate in the concept of mode specificity and bond selectivity in polyatomic systems. Until very recently, the main concern of those studies has been total reactivity and little attention has been paid to the mode-specific effects on the more detailed product-state and angular distributions. Conventional wisdom would anticipate that the fine detail should reveal a more pronounced mode dependency. However, a few recent studies showed that the product distributions could appear to be surprisingly insensitive to the modes of internal excitation of reagents. This counterintuitive finding led to a concept of loss of memory. Here, we present detailed experimental results in the reactions of the Cl atom with three distinct stretching-excited CH3D(vCH3 = 1) reagents. In conjunction with the previous reports on various aspects of this reaction, such a comprehensive set of data enables us to perform an in-depth examination of the validity of this new concept.