Chemiluminescence from the reactions of nitrogen and oxygen atoms with phosphorus vapour

Abstract

New chemiluminescence from the reactions of N + P₄ and O + P₄ has been observed. In the O-atom reaction the emission was assigned to the forbidden a ³Σ_u⁺–X ¹Σ_g⁺ transition of P₂ which has not been previously observed in the gas phase. Vibrational levels up to v′= 2 and v″= 8 were assigned in this spectrum and emission intensities generally agreed well with Franck–Condon factor calculations. In the N-atom reaction the emission arises from the well known A ¹Π–X ¹Σ⁺ system of PN in vibrational levels up to v′= 8. Approximate thermodynamic values show that the P₂ emission may well arise from the primary step of the reaction, but that the PN emission must arise from the reaction of secondary products.