| Molecular beam studies determined reaction products and natures of intermolecular interactions using dispersed chemiluminescence and the beam species' time of flight. Beam-gas reactions of phosphorus, antimony, bismuth, and manganese with ozone and fluorine, as well as reactions of calcium and copper with PCl 5 and ClF3 were studied.;Phosphorus atoms, antimony atoms, antimony dimers, and bismuth atoms form PO2, SbO2, BiO2, and probably SbO and BiO. Antimony atoms and dimers, and bismuth atoms produce chemiluminescence via two-step mechanisms, also, all atoms produce chemiluminescence through one-step mechanisms. The P atom one-step mechanism and the two-step mechanisms of antimony and bismuth proceed through barrierless potentials. The antimony atom and bismuth one-step mechanisms involve large barriers, 50 and 40 kJ mol-1, respectively. The bismuth atom two-step mechanism is strongly attractive, possibly harpooning at 2.8 A.;Antimony atoms were not observed to react with F2 in a single step, except as part of a two-step mechanism, yielding SbF2. Dimers were observed to proceed through two distinct one-step mechanisms, producing both SbF and SbF2. These reactions proceed through barrierless, attractive potentials.;Manganese atoms were observed to produce chemiluminescence through a one-step mechanism yielding MnF, and via a two-step mechanism yielding MnF 2. These reactions proceed through potentials with comparatively low barriers, roughly 2.4 to 3.7 kJ mol-1, and exhibit attractive forces. An electron jump may occur at a distance of about 3.3 A. Manganese reactions with ozone were observed to have a slightly attractive potential, with a very small barrier.;Reactions of Ca and Cu with ClF3 and PCl5 yield chemiluminescence from diatomic and larger polyatomic products. Calcium and Cu were only observed to react in one-step mechanisms. With ClF 3, Ca forms CaF* and CaF*2. Copper reacts with ClF3 to product CuF*. Copper and PCl 5 are believed to produce free to bound emission from CaCl**2, above the CuCl + Cl dissociation limit. |
