### Session S19: Undergraduate Session II

2:06 PM–3:18 PM, Monday, April 14, 2008
Hyatt Regency St. Louis Riverfront (formerly Adam's Mark Hotel), Room: Director's Row 47

Sponsoring Unit: SPS
Chair: Monica Plisch, American Physical Society

Abstract ID: BAPS.2008.APR.S19.5

### Abstract: S19.00005 : Probing the Unusual Thresholds of AlH+/AlD+ formation by Molecular Dynamic Simulations on MRCI Potential Energy Surfaces

2:54 PM–3:06 PM

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#### Author:

Nathan Brewer
(Sigma Pi Sigma/SPS- Union University)

In an experiment performed by P. Armentrout (Int. Rev. Phys. Chem. \textbf{1990}, $9$, 115), the Al$^{+}$ cation was accelerated into the various isotopic combinations of H$_{2}$ to form AlH$^{+}$ and AlD$^{+}$. It was found that the product-forming reactions proceed very inefficiently. The experiments also showed a reduction of $\sim$29{\%} in the threshold for the formation of AlD$^{+}$ from the HD reactant whereas all other AlH$^{+}$ and AlD$^{+}$ products formed at the same energetic threshold. Four previous theoretical attempts at capturing this unusual phenomenon have not been successful. The lowest energy singlet surfaces for the reaction of Al$^{+}$ with H$_{2}$ have been calculated at the multi-reference configuration interaction (MRCI) level of theory. The real/imaginary boundary of the symmetry-breaking b$_{2}$ vibrational mode was examined in three dimensions using Hessian matrices computed at a multi-configurational self-consistent field (MCSCF) level of theory. Molecular dynamic simulations numbering on the order of 10$^{7}$ were performed, sampling initial conditions reflective of the experiments. The simulations were run until they reached the location where the b$_{2}$ vibrational mode became unbound. A dissociation model was applied at these greatly compressed geometries to model the dissociation into AlH$^{+}$ and AlD$^{+}$ products.

To cite this abstract, use the following reference: http://meetings.aps.org/link/BAPS.2008.APR.S19.5