Reactive quenching of OH(A 2Sigma+) by D2 studied using crossed molecular beams.

Reactive quenching of OH(A 2Sigma+,v=0) by D2 forming HOD+D was studied in crossed molecular beams. The D atom products are primarily forward scattered relative to the incident D2. The dominant mechanism involves a direct reaction from relatively large impact parameters with approximately 88% of the available energy appearing in HOD internal excitation.

Reaction dynamics of CN + O2 --> NCO + O(3P2).

We have used oxygen Rydberg time-of-flight spectroscopy to carry out a crossed molecular beam study of the CN + O2 reaction at collision energies of 3.1 and 4.1 kcal/mol. The O(3P2) products were tagged by excitation to high-n Rydberg levels and subsequently field ionized at a detector. The translational energy distributions were broad, indicating that the NCO is formed with a wide range of internal excitation, and the angular distribution was forward-backward symmetric, indicating the participation of NCOO intermediates with lifetimes comparable to or longer than their rotational periods. Rice-Ramsperger-Kassel-Marcus modeling of the dissociation of NCOO to NCO + O suggests that Do(NC-OO) > or = 38 kcal/mol, which is consistent with several theoretical calculations. Implications for the competing CO + NO channel are discussed.

Photodissociation dynamics of N2O at 130 nm: the N2(A 3Sigmau +,B 3Pig)+O(3PJ = 2,1,0) channels.

Oxygen Rydberg time-of-flight spectroscopy was used to study the vacuum ultraviolet photodissociation dynamics of N(2)O near 130 nm. The O((3)P(J)) products were tagged by excitation to high-n Rydberg levels and subsequently field ionized at a detector. In agreement with previous work, we find that O((3)P(J)) formation following excitation to the repulsive N(2)O D((1)Sigma(+)) state produces the first two electronically excited states of the N(2) counterfragment, N(2)(A (3)Sigma(u) (+)) and N(2)(B (3)Pi(g)). The O((3)P(J)) translational energy distribution reveals that the overall branching ratio between N(2)(A (3)Sigma(u) (+)) and N(2)(B (3)Pi(g)) formation is approximately 1.0:1.0 for J = 1 and 2, with slightly less N(2)(B (3)Pi(g)) produced in coincidence with O((3)P(0)). The angular distributions were found to be independent of J and highly anisotropic, with beta = 1.5+/-0.2.