Experiments concerning phosphorus chemiluminescence

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Abstract
A variety of experimental techniques have been employed in a spectroscopic investigation of the strong visible chemiluminescence from the phosphine–nitrous oxide reaction system. Reaction was initiated by a fast electrical discharge in PH3/N2O mixtures over the pressure range 18–666 Torr. The predominant emission is a true continuum extending from a threshold wavelength at 3300 Å to beyond 1 μm. The results are consistent with the possible existence of a chemically formed (PO)2* exciplex molecule as the source of the visible continuum emission, but another molecular emitter containing only phosphorus and oxygen atoms, such as PO2, cannot be ruled out. Because of the possible use of this reaction system for a tunable, visible laser source, laser cavity tests and absorption and stimulated emission tests were carried out; these gave negative results. The photon yield from 3300 to 9000 Å was determined to vary linearly with pressure; a maximum yield of 8.5×10−3 was reached at the highest pressure investigated of 666 Torr. The broad spectral range of emission and low photon yield indicates that the ratio of stimulated emission to spontaneous emission did not exceed 0.02 at any wavelength shorter than 9000 Å.

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