Issue 43, 2017

Nonadiabatic quantum dynamics calculations of transition state spectroscopy of I + HI and I + DI reactions: the existence of long life vibrational bonding resonances

Abstract

We present the results of nonadiabatic quantum wave packet calculations to analyze the experimental transition state spectra for the I(2P3/2,1/2) + XI (X = H and D) hydrogen exchange reactions based on photodetachment of the IXI anion. We developed (3 × 3) diabatic potential energy surfaces that can reasonably describe the nonadiabatic transitions induced by spin–orbit interactions. A good agreement was obtained between theory and experiment and it was found that nonadiabatic transitions play a role in the reaction dynamics. We also found that the calculated spectra showed very sharp resonance states with a vibrational bonding character, where the resonance wavefunctions are highly localized around the transition state region. Our calculated results suggest that one may experimentally detect these vibrational bonding resonances using time-domain transition state spectroscopy techniques since those states have picosecond-order lifetimes.

Graphical abstract: Nonadiabatic quantum dynamics calculations of transition state spectroscopy of I + HI and I + DI reactions: the existence of long life vibrational bonding resonances

Supplementary files

Article information

Article type
Paper
Submitted
11 Aug 2017
Accepted
12 Oct 2017
First published
12 Oct 2017

Phys. Chem. Chem. Phys., 2017,19, 29125-29133

Nonadiabatic quantum dynamics calculations of transition state spectroscopy of I + HI and I + DI reactions: the existence of long life vibrational bonding resonances

T. Takayanagi, Phys. Chem. Chem. Phys., 2017, 19, 29125 DOI: 10.1039/C7CP05478E

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