Communication: Reactivity borrowing in the mode selective chemistry of H + CHD3 -> H-2 + CD3

Ellerbrock R, Manthe U. Communication: Reactivity borrowing in the mode selective chemistry of H + CHD3 -> H-2 + CD3. JOURNAL OF CHEMICAL PHYSICS. 2017;147(24): 241104.Quantum state-resolved reaction probabilities for the H + CHD3 -> H-2 + CD3 reaction are calculated by accurate full-dimensional quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree approach and the quantum transition state concept. Reaction probabilities of various ro-vibrational states of the CHD3 reactant are investigated for vanishing total angular momentum. While the reactivity of the different vibrational states of CHD(3 )mostly follows intuitive patterns, an unusually large reaction probability is found for CHD3 molecules triply excited in the CD3 umbrella-bending vibration. This surprising reactivity can be explained by a Fermi resonance-type mixing of the single CH-stretch excited and the triple CD(3 )umbrella-bend excited vibrational states of CHD3 . These findings show that resonant energy transfer can significantly affect the mode-selective chemistry of CHD3 and result in counter-intuitive reactivity patterns. Published by AIP Publishing