title: Collision-free photochemistry of methylazide: observation of unimolecular decomposition of singlet methylnitrene.
abstract: Methylazide photolysis at 248 nm has been investigated by ionizing photofragments with synchrotron radiation in a photofragmentation translational spectroscopy study. CH3N and N2 were the only observed primary products. The translational energy release suggests a simple bond rupture mechanism forming singlet methylnitrene, 1CH3N, and N2. Thus, these experiments reveal the unimolecular decomposition of this highly unstable species. We explain our observations through a mechanism which is initiated by the isomerization of 1CH3N to a highly internally excited methanimine H2C=NH isomer, which decomposes by 1,1-H2 elimination forming HNC+H2 as well as sequential H-atom loss (N-H followed by C-H bond cleavage), to form HCN. No evidence for dynamics on the triplet manifold of surfaces is found.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Santa Barbara, Santa Barbara, California 93106, USA. clarson@chem.ucsb.edu
authors.forename: Christopher
authors.initials: C
authors.lastname: Larson
authors.forename: Yuanyuan
authors.initials: Y
authors.lastname: Ji
authors.forename: Petros
authors.initials: P
authors.lastname: Samartzis
authors.forename: Alec M
authors.initials: AM
authors.lastname: Wodtke
authors.forename: Shih-Huang
authors.initials: SH
authors.lastname: Lee
authors.forename: Jim Jr-Min
authors.initials: JJ
authors.lastname: Lin
authors.forename: Chanchal
authors.initials: C
authors.lastname: Chaudhuri
authors.forename: Tao-Tsung
authors.initials: TT
authors.lastname: Ching