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Updated: Jan 1, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Photodissociation transition states characterized by chirped pulse millimeter wave spectroscopy
Kirill Prozument1,2, Joshua H Baraban1,3, P Bryan Changala4
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139.
Abstract:
The 193-nm photolysis of CH2CHCN illustrates the capability of chirped-pulse Fourier transform millimeter-wave spectroscopy to characterize transition states. We investigate the HCN, HNC photofragments in highly excited vibrational states using both frequency and intensity information. Measured relative intensities of J = 1-0 rotational transition lines yield vibrational-level population distributions (VPD). These VPDs encode the properties of the parent molecule transition state at which the fragment molecule was born. A Poisson distribution formalism, based on the generalized Franck-Condon principle, is proposed as a framework for extracting information about the transition-state structure from the observed VPD. We employ the isotopologue CH2CDCN to disentangle the unimolecular 3-center DCN elimination mechanism from other pathways to HCN. Our experimental results reveal a previously unknown transition state that we tentatively associate with the HCN eliminated via a secondary, bimolecular reaction.
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