Dissociation dynamics of the HOOO radical upon IR excitation: Nature of chemical bonding

PHYS 587

Craig Murray, crmurray@sas.upenn.edu, Erika L Derro, ederro@sas.upenn.edu, Timothy D. Sechler, sechler@sas.upenn.edu, and Marsha I Lester, milester@sas.upenn.edu. Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323
The vibrational predissociation dynamics of the atmospherically important HOOO radical have been investigated following initial excitation in the OH stretch fundamental and overtone transitions. HOOO was prepared in a supersonic free-jet by three-body association of photolytically-produced OH with O2 and vibrationally excited in the collision-free region of the expansion using tunable infrared radiation. The nascent OH X2ΠΩ v, N, ε products were probed with rotational and fine-structure resolution using laser-induced fluorescence. Vibrational predissociation is observed to occur exclusively with loss of a single quantum of OH stretch vibration, and produces apparently near-statistical rotational and spin-orbit distributions. A strong propensity for population of the Π(A′) Λ-doublets is observed, which is consistent with planar dissociation of the 2A″ HOOO parent and retention of the symmetry of the bonding orbital.
 

PHYS Poster Session - Computational Spectroscopy and Reaction Dynamics
7:30 PM-10:00 PM, Wednesday, April 9, 2008 Morial Convention Center -- Hall A, Poster

Sci-Mix
8:00 PM-10:00 PM, Monday, April 7, 2008 Morial Convention Center -- Hall A, Sci-Mix

Division of Physical Chemistry

The 235th ACS National Meeting, New Orleans, LA, April 6-10, 2008