1. PHOTOCHEMISTRY OF MATRIX- ISOLATED VINYL ACETATE KRISTA COHEN and C. A. BAUMANN Department of Chemistry The University of Scranton

2. Vinyl Acetate

3. Experimental Details Ar, Kr, N 2 (R:M 1:300, 1000, 2000) Ar, Kr, N 2 (R:M 1:300, 1000, 2000) irradiation after deposition (Hg/D 2 lamps) irradiation after deposition (Hg/D 2 lamps) IR: 100 scans 1.0 cm -1 resolution IR: 100 scans 1.0 cm -1 resolution CH 3 COOCHCH 2, CD 3 COOCDCD 2, CH 3 COOCHCH 2 CH 3 COOCHCH 2, CD 3 COOCDCD 2, CH 3 COOCHCH 2

4. Computational Details Gaussian 03W Gaussian 03W UB3LYP UB3LYP 6-311++G(2d,p) 6-311++G(2d,p) Scale factor: 0.966 Scale factor: 0.966 a Gaussian 03, Revision C.02, Frisch, M. J. et al. Gaussian, Inc., Wallingford CT, 2004; Becke, A. D. J. Chem. Phys. 1993, 98, 5648; Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785;

5. cis-trans cis-cis +15.4 kJ mol -1 trans-trans +28.6 kJ mol -1 Vinyl Acetate

13. Primary Step

14. CO, CO 2 and N 2 O Or a cyclic intermediate?

15. Succinaldehyde

20. Excited State PES 250 nm 200 nm T1T1 S3S3 T4T4 S1S1 S2S2 T3T3 T2T2 T5T5

21. Excited State PES 250 nm 200 nm S3S3 T4T4 S2S2 T5T5 Some (  *) states are dissociative along the ester bond.

22. Conclusions CH 2 CO, CO, CH 4, succinaldehyde and C O 2 CH 2 CO, CO, CH 4, succinaldehyde and C O 2 O product O product No apparent H/D isotope effect No apparent H/D isotope effect Some CO 2 arises from the vinyl moiety Some CO 2 arises from the vinyl moiety

23. Acknowledgments Petroleum Research Fund of the American Chemical Society Petroleum Research Fund of the American Chemical Society National Science Foundation National Science Foundation Research Committee Research Committee Faculty Development Board Faculty Development Board Luke Summa Luke Summa