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Title: Photodissociation dynamics of the N[sub 3] radical

Journal Article · · Journal of Chemical Physics; (United States)
DOI:https://doi.org/10.1063/1.465224· OSTI ID:6278011
; ; ; ;  [1]
  1. Department of Chemistry, University of California, Berkeley, California 94720 (United States) Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, California 94720 (United States)

The dissociation dynamics of the [ital [tilde B]] [sup 2][Sigma][sub [ital u]][sup +] state of N[sub 3] were investigated using fast radical beam photodissociation coupled with a new coincidence wedge-and-strip-anode particle detector. With this detector, detailed photofragment kinetic energy and angular distributions can be measured as a function of excitation energy. Calibration of the detector by studies of the predissociation of the O[sub 2] [ital B] [sup 3][Sigma][sub [ital u]][sup [minus]] state is discussed. Methods of extracting the center-of-mass kinetic energy and angular distributions are presented. The photodissociation results for N[sub 3] show that from the vibrationless level of the [ital [tilde B]] [sup 2][Sigma][sub [ital u]][sup +] state in N[sub 3], both spin-allowed [N[sub 3][r arrow]N([sup 2][ital D])+N[sub 2]([sup 1][Sigma][sub [ital g]][sup +])] and spin-forbidden [N[sub 3][r arrow]N([sup 4][ital S])+N[sub 2]([sup 1][Sigma][sub [ital g]][sup +])] dissociation processes occur. Bend excitation in the [ital [tilde B]] [sup 2][Sigma][sub [ital u]][sup +] state, however, enhances the spin-allowed dissociation process considerably. The kinetic energy distributions reveal partially resolved vibrational structure in the N[sub 2] fragment, and indicate substantial rotational excitation of the N[sub 2]. This implies that bent geometries play a major role in the dissociation of the N[sub 3] [ital [tilde B]] state. Possible mechanisms for the spin-forbidden and spin-allowed dissociation channels are discussed.

DOE Contract Number:
AC03-76SF00098
OSTI ID:
6278011
Journal Information:
Journal of Chemical Physics; (United States), Vol. 99:4; ISSN 0021-9606
Country of Publication:
United States
Language:
English