Imaging the Mode-Specificity in Cl + CH₃D(v₁-I, v₁-II, v₄ = 1; |jK⟩ = |10⟩) → CH₂D(4₁) + HCl(v)

We report a crossed-beam imaging experiment on the title reactions at two collisional energies (E_c) of 5.3 and 10 kcal mol^-1. Both the integral cross sections relative to the ground-state reactivity and the differential cross sections were measured and compared. We found that one-quantum excitations of the CH₃-stretching vibrations of the CH₃D reagent exerted profound mode-specificity in forming the umbrella-mode-excited CH₂D(4₁) products with the vibrational efficacy of v₄ > v₁-I > v₁-II at both E_c values. The concomitantly formed HCl(v) coproducts were vibrationally cold. Interestingly, the branching ratios of (v = 1)/(v = 0) appeared invariant to the initial stretch-modes of excitation at E_c = 5.3 kcal mol^-1, yet exhibited a pronounced mode-specific dependency in the order of v₁-II > v₁-I > v₄ at E_c = 10.3 kcal mol^-1. This large and E_c-dependent disparity between the two Fermi-coupled reagents, v₁-I and v₁-II, is particularly significant and could be another facet─in addition to that in the recently reported vibrational enhancement factors─of the Fermi-phase-induced interference effect manifested in the product vibrational branching ratio. The pair-correlated angular distributions (v_CH2D, v_HCl)_s = (4₁, 0)_s in the three stretch-excited reactions were globally alike and resembled that of the ground-state reaction pair (0₀, 0)_g, suggestive of a direct abstraction mechanism of the peripheral type. This is in sharp contrast to all other vibrationally excited pairs of (1₁, 0)_s, (3₁, 0)_s, and (6₁, 0)_s previously reported in the CH₂D + HCl isotopic channel, for which both the direct abstraction and a time-delayed resonance pathway partake.