Ground state dynamics of vinoxy: Computational and experimental study

PHYS 437

D I G Bennett,, Department of Chemistry, Univeristy of Chicago, 5640 S Ellis Ave, RI 211, Chicago, IL 60637, Laurie J. Butler, Department of Chemistry and The James Franck Institute, University of Chicago, 5640 S. Ellis Ave., Chicago, IL 60637, and H-J. Werner, Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany.
On the ground state surface of vinoxy (CH2CHO) the two lowest energy reaction barriers are CH2CHO → CH2CO + H and CH2CHO → CH3CO. Previous work by Miller, et al. has shown that the isomerization channel completely dominates at energies spanning both barrier heights. Young and Yarkony's previous calculations at the multi-reference configuration interaction (MRCI) level predicted a large difference between the two reaction barriers (~4 kcal/mol) and a conical intersection in the region at energies too high to result in significant non-adiabatic effects. The current work explores the change in barrier heights and non-adiabatic coupling terms along the minimum energy paths resulting from extending the active space and reconsidering the state-averaging method of the MRCI calculations. An adiabatic excitation energy to the first excited state in found and compared to previous results. Finally, these calculations are used to assist in modeling the previous experimental results.

Poster Session
7:30 PM-10:00 PM, Wednesday, 13 September 2006 Moscone Center -- Hall D, Poster

Division of Physical Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006