The dynamics of the reaction, Y + O2--> YO + O was studied by using the crossed-beam technique at several collision energies from 10.3 to 52.0 kJ mol(-1). The Y atomic beam was generated by laser vaporization and crossed with the O2 beam at a right angle. Among the energetically accessible electronic states of YO, the formation of the A2Pi and A'2Delta states was observed by their chemiluminescence at all collision energies. By analyzing the chemiluminescence spectra of YO(A2Pi(1/2,3/2)-X2Sigma+), vibrational state distributions and relative populations of spin-orbit states were determined for YO(A2Pi(1/2,3/2)). At low collision energies, the vibrational distributions agree quite well with those expected from the statistical energy partitioning, while a little deviation from the statistical expectation was observed at the highest energy, 52.0 kJ mol(-1). The populations of two spin-orbit states are in good agreement with the statistical expectations at all collision energies. The vacuum ultraviolet laser-induced fluorescence (VUV-LIF) technique was employed to determine the distributions of spin-orbit states of the product O(3P(J)) at two collision energies, 20.7 and 52.0 kJ mol(-1). The line shapes of the O atom transitions were analyzed to determine relative branching ratio of the ground state to the excited states of YO, i.e. YO(X2Sigma+)+ O(3P(J))vs. YO(A2Pi and A'2Delta)+ O(3P(J)). The results showed that the electronically excited YO was formed with comparable amount with the ground state which is statistically more favorable, and suggested the occurrence of two mechanisms taking place in the title reaction.

The dynamics of the reaction, V(a 4FJ)+NO-->VO(X 4Sigma-)+N was studied by using a crossed-beam technique at 16.4 kJ/mol of collision energy. The V atomic beam was generated by laser vaporization and crossed with the O2 beam at a right angle. The laser-induced fluorescence (LIF) for the transition of VO(B 4Pi-X 4Sigma) was used to determine the rotational state distribution of the reaction product in the vibrational ground state. Almost pure V(a 4FJ) beam was obtained by using the mixture of NH3 with N2 as a carrier gas. Comparing the LIF spectra of VO measured for two carrier gases, i.e., NH3N2 and pure N2, it was concluded that the vibrational ground state of VO(X 4Sigma-) is formed almost entirely from the reaction of V(a 4FJ) and the contribution of the metastable V(a 6DJ) is negligible. The observed rotational distribution was similar to a statistical prior prediction, and suggested that the title reaction proceeds via a long-lived intermediate, which is consistent with an electron transfer mechanism.

The vacuum ultraviolet laser-induced fluorescence technique was employed to detect the oxygen atoms formed by the reaction, Al+O(2)--> AlO+O. The measurements were carried out under the crossed-beam condition at 12.2 kJmol of collision energy. The relative populations of three spin-orbit states of O((3)P(J)) were determined to be 3.8, 1.0, and 0.2 for J=2, 1, and 0, respectively. They show nonstatistical populations, i.e., more population in O((3)P(2)) and less population in O((3)P(0)) than the statistical expectation. These populations were almost identical for two Al beam conditions where the relative concentrations of two spin-orbit states of Al, (2)P(1/2), and (2)P(3/2), are different. These results suggest that the reaction of Al with O(2) proceeds via an intermediate complex where the memory of the initial spin-orbit state is lost. Deviation from the statistical population of O((3)P(J)) implies the occurrence of the interaction among potential surfaces in the exit channel.