CHEMILUMINESCENCE FROM THE REACTIONS OF NITROGEN AND OXYGEN-ATOMS WITH PHOSPHORUS VAPOR

New chemiluminescence from the reactions of N + P-4 and O + P-4 has be en observed. In the O-atom reaction the emission was assigned to the f orbidden a (3) Sigma(u)(+)-X(1) Sigma(g)(+) transition of P-2 which ha s not been previously observed in the gas phase. Vibrational levels up to v' = 2 and v '' = 8 were assigned in this spectrum and emission in tensities generally agreed well with Franck-Condon factor calculations . In the N-atom reaction the emission arises from the well known A (1) Pi-X(1) Sigma(+) system of PN in vibrational levels up to v' = 8. App roximate thermodynamic values show that the P-2 emission may well aris e from the primary step of the reaction, but that the PN emission must arise from the reaction of secondary products.