Quenching and enhancement of aroyl luminescence in excited nitrogen.
This study investigates both decreases and increases of aromatic carbonyl phosphorescence in excited nitrogen, i.e., in a gas-chromatographic device called the aroyl luminescence detector (ALD). The ALD responds, with nigh specificity, to subpicogram amounts of strongly phosphorescing aroyls. Aroyl response may, however, be quenched by coeluting peaks or gaseous impurities. This deleterious effect has been investigated with O2, H2, CH4, and C3H8 as model quenchers. Aroyl phosphorescence is more severely quenched than the nitrogen background, i.e., the so-called second-positive system, N2 (C 3 pi u)-->N2 (B 3 pi g). Oxygen, while being the strongest among the tested quenchers of aroyl phosphorescence, is the weakest quencher of nitrogen emission. The efficiency of various quenchers is similar for aroyl compounds of similar structure. It differs, however--though not by more than a factor of 2--among aroyls of different chemical types. In contrast to these intensity-reducing effects, aroyl phosphorescence is significantly enhanced by the addition of argon to (the carrier and excitation gas) nitrogen. It is proposed that the reaction sequence Ar*(3P0,2) + N2-->N2(C)*-->N2(B)* + hv-->N2(A)* + hv results in an increased yield of the metastable N2(A 3 sigma u+) state (this state being considered responsible for the n-->pi* excitation of aroyl compounds via an efficient triplet-triplet energy-transfer process).