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THEORETICAL STUDIES OF THE ROLE OF VIBRATIONAL EXCITATION ON THE DYNAMICS OF THE HYDROGEN-TRANSFER REACTION OF F(²P) + HCl rightarrow

FH + Cl(²P).

SARA E. RAY, GÉ W. M. VISSERS AND ANNE B. MCCOY, Department of Chemistry, The Ohio State University, Columbus, OH 43210.

Hydrogen-transfer reactions are probed through vibrational excitation of the HCl bond in the pre-reactive F cdots HCl complex. Such open-shell species provide a challenge for quantum dynamical calculations due to the need to take into account multiple potential energy surfaces to accurately describe the system.

A three-dimensional, fully-coupled potential energy surface has been constructed based on electronic energies calculated at the multireference configuration interaction+Davidson correction (MRCI+Q) level of theory with an aug-cc-pVnZ (n=2,3,4) basis. Spin orbit calculations have also been included.

Here we present the results of time-dependent quantum wave packet calculations on the asymmetric hydrogen-transfer reaction of F(²P) + HCl. In these calculations, the reaction is initiated by vibrationally exciting the HCl stretching motion in the pre-reactive F cdots HCl complex. The wave packet is propagated on the coupled potential energy surfaces. Product state distributions were calculated for reactions initiated in the first three vibrationally excited states of HCl, v=1-3.