1. Water Solvation of Copper Hydroxide Brett Marsh-UW Madison

2. Background Copper Catalytic Relatively cheap Abundant CuOH-Possible water splitting catalyst

3. Experiment Electrospray Needle Cryogenic ion trap (10K) For cooling and H 2 -tagging Ion steering optics Flight Tube Reflectron Tunable infrared laser 600-4500 cm -1 Capillary Skimmer Radio-frequency ion guides Ion reaction cell LN 2 cooled (77-350K) Spectroscopy laser Pulsed valves

4. Ion Trapping and Tagging H 2 has ideal binding energy (~400 cm -1 typically) and vapor pressure at trap temperature (10 K) H 2 tagging may produce multiply tagged species M.Z. Kamrath, R.A. Relph, T.L. Guasco, C.M. Leavitt, M.A. Johnson, Int. J. Mass. Spec. 2011, 300, 91-98

5. Predissociation Spectroscopy E. Garand et. al. Phys. Chem. Chem. Phys., 2012,14, 10109–10113

6. Experiment Electrospray Needle Cryogenic ion trap (10K) For cooling and H 2 -tagging Ion steering optics Flight Tube Reflectron Tunable infrared laser 600-4500 cm -1 Capillary Skimmer Radio-frequency ion guides Ion reaction cell LN 2 cooled (77-350K) Spectroscopy laser Pulsed valves

7. Results By varying voltages in ion source multiple species of interest can be selected for study

8. Results-CuOH(H 2 O) + Addition of 2 nd deuterium tag distorts spectrum Strong H 2 O-D 2 interaction? Multiple conformations for 1 tag complex?

9. Results-CuOH(H 2 O) + CAM-B3LYP/6-311+G(d,p) level of theory

10. Results-CuOH(H 2 O) 2 + Severe peak suppression occurs after attachment of 2 nd deuterium molecule Possible solvent assisted isomerization?

11. Results-CuOH(H 2 O) 2 + Isomers separated by ~1450 cm -1 Multiple lines hidden under same peak? Probe for H-bond stretches (2800- 3100 cm -1 ) CAM-B3LYP/6-311+G(d,p) level of theory

12. Solvent Assisted Isomerization Excess solvation energy (in this case from D 2 ) can push the molecule into a more stable well Excess D 2 then evaporates to leave isomer 2+2D 2

13. Results-CuOH(H 2 O) 2 + Strong free H 2 O interaction with D 2 tag Theory matches well with experimental spectrum CAM-B3LYP/6-311+G(d,p) level of theory

14. Results-CuOH(H 2 O) 2 + CAM-B3LYP/6-311+G(d,p) level of theory

15. Results-CuOH(H 2 O) 3 + Addition of 2 nd deuterium tag seems to have no effect on spectrum

16. Conclusions Hydrogen tags can not be assumed to offer little perturbation in metal species Attachment of tags may distort the isomeric composition of ions of interest

17. Future Work Electrospray Needle Cryogenic ion trap (10K) For cooling and H 2 -tagging Ion steering optics Flight Tube Reflectron Tunable infrared laser 600-4500 cm -1 Capillary Skimmer Radio-frequency ion guides Ion reaction cell LN 2 cooled (77-350K) Spectroscopy laser Pulsed valves Tunable infrared laser 600-4500 cm -1

18. Acknowledgements Crim Group Garand Group University of Wisconsin Chemistry Department