Measurement of Helical Trajectories in Chemical Reactions by Ion Imaging

During the first year of this grant we developed methods to measure the sense of rotation of the nitric oxide molecule (NO) using a circularly polarized laser probe and with ion imaging detection. The method was applied to the measurement of the correlation of rotational angular momentum orientation with recoil direction in the photodissociation of NO{sub 2}. [''Detection of ''ended'' NO recoil in the 355 nm NO2 photodissociation mechanism'', V.K. Nestorov and J.I. Cline, J. Chem. Phys. 111, 5287-5290 (1999)]. The photodissociation work was performed at the University of Nevada with additional, partial support from NSF. In the summer of 1999 this technique was transported to and implemented at the Combustion Research Facility at Sandia National Laboratory in Livermore, CA in a study of rotationally inelastic collisions of NO molecules with Ar atoms. The summer 1999 experiments at Sandia demonstrated that it is possible to detect collision-induced rotational alignment (preferred planes of rotation) for product molecules. During the late summer and fall of 1999 the P.I. and student James Barr developed a theoretical method for quantifying the angular momentum alignment and for extracting it from ion images. During the winter and spring of 2000 (January-May) the P.I. was in residence at Sandia National Laboratory in Livermore during a sabbatical leave from the University of Nevada. During this time the P.I. collaborated with Sandia P.I. Dr. David Chandler and Sandia postdoctorals Thomas Lorenz and Elisabeth Wade in experiments measuring both rotational alignment and rotational orientation (preferred senses of rotation) in collisions of NO with Ar. Graduate student James Barr continued these experiments at Sandia through the end of June 2000. The success of our experimental techniques for measuring collisional alignment and the theoretical methods we have developed for extracting quantitative alignment parameters from ion images. Spectroscopic probing of products by resonance-enhanced multiphoton ionization (REMPI) detected by ion imaging is a powerful method for measuring the product state-resolved differential cross section (DCS) of bimolecular scattering reactions. Polarization of the REMPI probe light also makes imaging data potentially sensitive to product angular momentum polarization, as is well known from imaging studies of photodissociation. We exploit this sensitivity to obtain the state-resolved product angular momentum polarization as a function of recoil angle. Previous measurements of molecular angular momentum polarization in bimolecular scattering have either been constrained to detection in the scattering plane or have averaged around the azimuthal angle of the recoil velocity vector in the collision frame. Imaging detection captures the entire product recoil velocity sphere, enabling a more complete determination of product angular momentum polarization than is possible for experiments of lower detection dimensionality