Abstract
The creation of electronically excited species by the 193 nm excimer laser photolysis of PCl 3 and PBr 3 has been studied. In addition to halogen and phosphorus atomic lines, emission is detected from highly excited states of Cl 2 and Br 2, respectively, formed by a two-photon process. We also observe previously unreported emission systems which we attribute to the A 2A 1→ X 2B 1 transitions of PCl 2 and PBr 2, which are formed by a single-photon process. The PCl 2 and PBr 2 A → X emission spectra are broad and structureless, peaking at ≈460 and 527 nm with short wavelength thresholds of ≈370 and 510 nm, respectively. The A states of PCl 2 and PBr 2 have long radiative lifetimes (29±6 μs and 21±9 μs, respectively) and are very efficiently quenched by PCl 3 or PBr 3.
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