Photolysis of Cyclobutane at Photon Energies Below and Above the Ionization Energy

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Abstract
The photolysis of cyclo‐C4H8 and of cyclo‐C4H8—cyclo‐C4D8 mixtures has been investigated at 1470 and 1236 Å in the absence and presence of NO. In addition, a series of experiments carried out in which H2S was used as a free‐radical interceptor in the photolysis of cyclo‐C4D8 at 1236 Å. Approximately 90% of the observed products can be accounted for by the primary process: C4H8+hv→2C2H4. The extent to which the internally excited ethylene formed in this process will decompose further increases with diminishing pressure and wavelength. The photolysis of cyclobutane has been investigated at energies above the ionization energy (I.E.=10.3 eV), using the argon resonance lines at 11.54 and 11.72 eV. It is shown that when NO is added to the system, cis‐2‐butene, trans‐2‐butene, and 1‐butene are major products. These butenes are, however, not produced when NO (I.E.=9.25 eV) is replaced by O2 (I.E.=12.1 eV) and are only formed in trace amounts when no additives are present. It is suggested that the parent ion acquires the olefinic structure and undergoes charge exchange with NO.
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