1. Carbon Dioxide Clusters and Copper Complexes Formed in Argon Matrices Michael E. Goodrich & David T. Moore Chemistry Department, Lehigh University Bethlehem PA, 18015 1

2. Introduction CO Oxidation on metal center Cu(CO) m (O 2 ) n complexes difficult to form What happens when both CO and CO 2 are in the matrix Identify CO 2 species in matrix Identify Cu(CO)(CO 2 ) clusters 2

3. Experimental 3 Deposit 0.02-0.5% CO 2 in Argon at 10sccm and 10- 20K ~4 nA beam of Cu - balanced with a 25-50eV cationic counter ion (Ar + /SF 5 + )

4. CuCO 2 and CO 2 Clusters 4 CuCO 2 - CO 2 - (CO 2 - )(CO 2 ) C2O4-C2O4- 10K Deposition of 0.5% CO 2 in Argon with Cu - and Ar + Observe conversion of anionic CO 2 cluster to oxalate- like C 2 O 4 - No apparent conversion to anionic CO 2 peaks Zhou, M.; et al. J. Phys. Chem. A. 103, 2013. (1999) Zhou, M.; Andrews, L. J. Chem. Phys. 110, 2414 (1999)

5. CO 2 Symmetric Stretch Region 5 (CO 2 ) 2 (CO 2 ) 2 + CuCO 2 - 10K Deposition of 0.5% CO 2 in Argon with Cu - and Ar + Minimal changes upon irradiation and annealing Zhou, M.; et al. J. Phys. Chem. A. 103, 2013. (1999) Castano, J.A.G.; et al. J Mol. Structure 881, 68. (2008).

6. Effect of Counter Ion Choice on CO 2 cluster formation 6 SF 5 + shuts down the formation of cationic CO 2 clusters No presence of anionic clusters in SF 5 + spectrum High energy argon increases formation of cationic CO 2 clusters SF 6 Anionic clusters present upon deposition of Ar + suggesting formation is necessary for charge balance

7. Matrix Containing CO and CO 2 7 0.02% CO & CO 2 deposited at 20K No presence of CuCO 2 - Cu(CO) 2 CuCO - Cu(CO) 2 - Cu(CO) 3 - Cu(CO) 3 CuCO C2O3-C2O3- Peaks at 1701 and 1793 cm -1 assigned to C 2 O 3 - Zhou, M.; Andrews, L. J. Chem Phys. 111, 4548 (1999) Zhou, M.; et al. J. Chem. Phys. 112, 7089 (2000).

8. 8 Matrix Containing CO and CO 2 Small CuCO 2 - peak when CO 2 concentration is higher than CO No evidence of ternary Cu(CO)(CO 2 ) complexes

9. Conclusions and Future Work Identified Copper Carbon Dioxide Clusters and Ionic Carbon Dioxide clusters in an argon matrix Can control ionization pathways based on counter ion choice Further attempts to form Cu(CO)(CO 2 ) clusters and CuCO 2 clusters with CO present in matrix 9