Journal of Physical Chemistry A, Vol.123, No.8, 1514-1520, 2019
Effects of Stretching Excitations in Cl + CH3D(v(4), v(1)-I, v(1)-II=1): As the Cl Atom Attacks the Unexcited C-D Bond
The title reactions were studied at two collisional energies (E-c) in a crossed-beam product-imaging experiment. We found that all three initial CH stretching excitations suppress the reactivity toward the abstraction of the unexcited D atom. In terms of vibrational suppression factor, sigma(s)/sigma(g), the product channels of CH3(0(0)/4(1)) + DCl and CH3(1(1)/3(1)) + DCl show opposite mode-specific trends. However, the angular distributions of both channels are nearly identical to that of the ground-state reaction at the same E-c, regardless of the initial reactant states. Tentatively, we ascribed these two observations to a vibrationally induced narrowing effect of the attack angle near the barrier to reaction. As for the DCl coproduct state distributions, the two channels are distinct but show little mode-specific difference. When CH3(0(0)) is probed, the DCl coproduct peaks at v = 1 are accompanied by substantial rotational excitation, whereas the DCl products associated with CH3(1(1)/3(1)) are both vibrationally and rotationally cold. We attributed the different (correlated) energy disposals to a manifestation of trajectory bifurcations in the postbarrier region, with a vibrationally nonadiabatic pathway leading to CH3(0(0)) + DCl(v = 1) and the other adiabatically to the CH3(1(1)/3(1)) + DCl(v = 0) channel. For both pathways the initial CH stretching excitation acts as a conserved mode by preferentially retaining one quantum of vibrational excitation in the reaction.