Electronic polarization effects in the dynamics of the F/F*+ H2 reaction

PHYS 31

Marcelo P. de Miranda, m.miranda@leeds.ac.uk1, F. J. Aoiz2, Vicente Sáez Rábanos3, François Lique, francois.lique@obspm.fr4, and Millard H. Alexander, mha@umd.edu4. (1) School of Chemistry, University of Leeds, Leeds, LS2 9JT, United Kingdom, (2) Departmento de Quimica Fisica, Universidad Complutense, Facultad de Quimica, Ciudad Universitaria s/n, 28040 Madrid, Spain, (3) Departamento de Quimica y Bioquimica, Universidad Politecnica de Madrid, Escuela Tecnica Superior de Ingenieros de Montes, Madrid, 28040, Spain, (4) Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742-2021
No stereodynamics study has yet considered the role of electronic polarization in bimolecular collisions involving open-shell species. In our talk we will present the first results from our work on this problem. Using scattering matrices recently obtained by the M.H.Alexander group through time-independent, multistate, fully quantum scattering calculations for the F (2P3/2)/F*(2P1/2)/+D2 reaction and also our recently-developed theory of canonical reaction mechanisms, we are able to include all angular momentum vectors in the description of the F/F*+D2 reaction stereodynamics and also to disentangle the independent mechanisms contributing to it. This leads to detailed and quantitative information on how the electronic polarization of the fluorine atom influences reactivity. Given the recent advances by the R.N.Zare and P.T.Rakitzis groups concerning experimental production and control of electronically polarized atoms, it is likely that comparison of theory and experiment on the stereodynamics of reactions involving open-shell species will soon become a hot topic.
 

Electronic Structure and Reaction Dynamics of Open-shell Species
8:00 AM-12:05 PM, Sunday, April 6, 2008 Morial Convention Center -- Rm. 345, Oral

Division of Physical Chemistry

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