Photoinitiated decomposition of substituted ethylenes: The photodissociation of vinyl chloride and acrylonitrile at 193 nm
- Lawrence Berkeley National Lab., CA (United States); and others
Ethylene and its substituted analogues (H{sub 2}CCHX) are important molecules in hydrogen combustion. As the simplest {pi}-bonded hydrocarbons these molecules serve as prototypical systems for understanding the decomposition of this important class of compounds. The authors have used the technique of photofragment translational spectroscopy at beamline 9.0.2.1 to investigate the dissociation of vinyl chloride (X=Cl) and acrylonitrile (X=CN) following absorption at 193 nm. The technique uses a molecular beam of the reactant seeded in helium which is crossed at 90 degrees with the output of an excimer laser operating on the ArF transition, 193.3 nm. The neutral photoproducts which recoil out of the molecular beam travel 15.1 cm where they are photoionized by the VUV undulator radiation, mass selected, and counted as a function of time. The molecular beam source is rotatable about the axis of the dissociation laser. The authors have directly observed all four of the following dissociation channels for both systems: (1) H{sub 2}CCHX {r_arrow} H + C{sub 2}H{sub 2}X; (2) H{sub 2}CCHX {r_arrow} X + C{sub 2}H{sub 3}; (3) H{sub 2}CCHX {r_arrow} H{sub 2} + C{sub 2}HX; and (4) H{sub 2}CCHX {r_arrow} HX + C{sub 2}H{sub 2}. They measured translational energy distributions for all of the observed channels and measured the photoionization onset for many of the photoproducts which provided information about their chemical identity and internal energy content. In the case of acrylonitrile, selective product photoionization provided the ability to discriminate between channels 2 and 4 which result in the same product mass combination.
- Research Organization:
- Lawrence Berkeley Lab., CA (United States)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 603616
- Report Number(s):
- LBNL--39981; ON: DE97007345
- Country of Publication:
- United States
- Language:
- English
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