A new approach toward transition state spectroscopy

Kirill Prozument; Rachel Glyn Shaver; Monika A. Ciuba; John S. Muenter; G. Barratt Park; John F. Stanton; Hua Guo; Bryan M. Wong; David S. Perry; Robert W. Field

doi:10.1039/C3FD20160K

A new approach toward transition state spectroscopy

Kirill Prozument,^a Rachel Glyn Shaver,^a Monika A. Ciuba,^b John S. Muenter,^c G. Barratt Park,^a John F. Stanton,^d Hua Guo,^e Bryan M. Wong,^f David S. Perry^g and Robert W. Field*^a

Author affiliations

* Corresponding authors

^a MIT, Department of Chemistry, Cambridge, MA 02139
E-mail: kuyanov@mit.edu, rshaver@mit.edu, barratt@mit.edu, rwfield@mit.edu

^b Arizona State University, Department of Chemistry and Biochemistry, Tempe, AZ 85287-5601
E-mail: monika.ciuba@asu.edu

^c University of Rochester, Department of Chemistry, Rochester, NY 14627
E-mail: muenter@chem.rochester.edu

^d University of Texas at Austin, Department of Chemistry and Biochemistry, Austin, TX 78712
E-mail: jfstanton@mail.utexas.edu

^e University of New Mexico, Department of Chemistry, Albuquerque, NM 87131
E-mail: hguo@unm.edu

^f Sandia National Laboratories, Materials Chemistry Department, Livermore, CA 94550
E-mail: usagi@alum.mit.edu

^g The University of Akron, Department of Chemistry, Akron, OH 44325-3601
E-mail: dperry@uakron.edu

Abstract

Chirped-Pulse millimetre-Wave (CPmmW) rotational spectroscopy provides a new class of information about photolysis transition state(s). Measured intensities in rotational spectra determine species-isomer-vibrational populations, provided that the rotational populations can be thermalized. The formation and detection of S₀ vinylidene is discussed in the limits of low and high initial rotational excitation. CPmmW spectra of 193 nm photolysis of vinyl cyanide (acrylonitrile) contain J = 0–1 transitions in more than 20 vibrational levels of HCN and HNC, but no transitions in vinylidene or highly excited local-bender vibrational levels of acetylene. Reasons for the non-observation of the vinylidene co-product of HCN are discussed.

This article is part of the themed collection: Photo-initiated Quantum Molecular Dynamics

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A new approach toward transition state spectroscopy

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