Crossed jet reactive scattering dynamics of F+H(2)O-->HF(v,J)+OH:HF(v,J) product quantum state distributions under single-collision conditions.
Reactive scattering dynamics of F+H(2)O-->HF+OH have been investigated under single-collision, crossed, supersonic jet conditions at 5.4(1.3) kcalmol, and nascent HF(v,J) rovibrational populations (v<or=2, J<or=17) have been observed via high resolution IR laser absorption methods. Vibrational populations are highly inverted, with 75(2)% and 21(5)% of the observed HF product formed in v=1 and 0, respectively. Small but finite branching [5(1)%] into the v=2 manifold is observed, which is accessible only via the additional center of mass collision energy in the crossed jets. Despite energy constraints associated with substantial vibrational excitation, the reaction dynamics also lead to rotationally hyperthermal HF, with populations observed up to near the energetic limit for each of the v=0,1,2 vibrational manifolds. The trends in these nascent product rovibrational distributions are interpreted in terms of ab initio predictions of a strongly bent, early-barrier transition state and long-range dipole-dipole interactions in the exit channel.
Zolot
Alexander M
AM
JILA, National Institute of Standards and Technology and University of Colorado, Boulder, Colorado 80309, USA.
Nesbitt
David J
DJ