Stretching-mode specificity in the Cl + CH3D(v1-I, v1-II, and v4 = 1; |jK〉) reactions: dependency on the initial |jK〉 selectivity

Abstract

The title reactions were studied at a collisional energy of 5.4 kcal mol⁻¹ in a crossed-beam product-imaging experiment. The dynamics attributes of the dominant ground-state CH₂D(0₀) and the accompanied C–D bend-excited CH₂D(6₁) products were imaged in reactions with totally 16 ro-vibrationally selected states of the CH₃D(v_i, |jK〉) reagents. We found that all three vibrational excitations yielded marked |jK〉-dependent rate-enhancements in forming the (0₀, 0/1)_s product pairs. Furthermore, for a given rotational |jK〉-mode, a vibrational-mode propensity of v₄ > v₁-I > v₁-II in rate promotion and a clear manifestation of the Fermi-phase-induced interference effect of the latter two were observed. Compared to the reactivity of the rotationless state |jK〉 = |00〉, a minute rotational-excitation of all three stretch-excited CH₃D(v_i = 1) reagents could yield significantly higher reaction rates for the product pair (0₀, 0)_s, but not so for (0₀, 1)_s. The signals in forming the (6₁, 0)_s pair were clearly notable but smaller than that of the ground-state reaction product pair, (0₀, 0)_g. An opposite propensity of v₁-II ≈ v₁-I > v₄ with a milder dependency on the initial |jK〉-states was observed. The angular distributions of the (0₀, 0)_s pairs were nearly identical for all ro-vibrationally excited reagents, displaying the typical trait for a direct abstraction of the rebound mechanism. Similar distributions were found for the (6₁, 0)_s pairs; yet, both pairs deviated substantially from the peripheral feature of the ground-state reaction pair of (0₀, 0)_g. Those of the (0₀, 1)_s pairs in reactions with v₄-excitation featured a prominent forward-peaking distribution—suggestive of a time-delayed, resonance-mediated pathway, again with little dependency on the initial |jK〉-states. As for the reactions with the two Fermi-dyads, v₁-I and v₁-II, albeit showing globally similar distributions to that for v₄, a substantial variation with the initial rotational-mode excitation could be discerned in the forward-peaking features. To unravel the impact of the Fermi-phase on the |jK〉-dependent attributes, we adopted a comparative approach by contrasting the observations in reactions with the Fermi-dyad reagents (the superposition states) to those with the pure-state reagents. Remarkable distinctions are unveiled and elucidated with the unexplained results explicitly pointed out, which call for future theoretical investigations for deeper understanding.