Control of bimolecular reactions: Bond-selected reaction of vibrationally excited CH[sub 3]D with Cl ([sup 2]P[sub 3/2])

Yoon, Sangwoon; Holiday, Robert J.; Crim, F. Fleming
September 2003
Journal of Chemical Physics;9/1/2003, Vol. 119 Issue 9, p4755
Academic Journal
Selective vibrational excitation permits control of the outcome of a reaction with two competing channels. The thermal reaction of CH[sub 3]D with Cl ([sup 2]P[sub 3/2]) yields two reaction products: CH[sub 3] from the D-atom abstraction and CH[sub 2]D from the H-atom abstraction. We prepare the first overtone of the C–D stretching vibration (2ν[sub 2]) at ∼4300 cm-1 and react the vibrationally excited molecule with photolytic Cl atoms. The 2+1 resonance enhanced multiphoton ionization spectra for the products show that the 2ν[sub 2] vibrational excitation of CH[sub 3]D exclusively increases the probability of breaking the C–D bond, yielding CH[sub 3] but no CH[sub 2]D. By contrast, vibrational excitation of the combination of the antisymmetric C–H stretch and CH[sub 3] umbrella (ν[sub 4]+ν[sub 3]) vibrations, which has total energy similar to that of 2ν[sub 2], preferentially promotes the H-atom abstraction reaction to produce CH[sub 2]D over CH[sub 3]. The vibrational action spectra for the two products permit the separation of the two sets of interleaved transitions to give band origins and rotational constants of the 2ν[sub 2] state and the ν[sub 4]+ν[sub 3] state of CH[sub 3]D. © 2003 American Institute of Physics.


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