1. Molecular Hydrogen attached to Metal Cations Evan Bieske School of Chemistry University of Melbourne

3. Hi-Res Spectroscopy vs Blobology Viktoras Dryza Berwyck Poad Alexei Buchachenko Jacek Klos Corinna Emmeluth Chris Thompson Brian Adamson Neville Coughlan Bob Continetti Gabe Da Silva Australian Research Council $$$ Cl - M + =Li +, Na +, Mg +, B +, Al +, Mn +, Zn +, Cr + +

4. Hydrogen Power

6. Hydrogen Storage - the bad times

8. MOFs, zeolites and other junk

11. Gas Phase Binding Enthalpies Bowers, Kemper, Bushnell (1990-2000)

12. Theory vs Experiment - Na + -H 2 D 0 =842 cm -1 para H 2 D 0 =888 cm -1 ortho H 2 D 0 =860±70 cm -1 exp Bowers Alexei Buchachenko Jacek Klos RCCSD(T)/aug-cc-pVQZ+bond functions -1184 cm -1 -183cm -1 ΔK a =0 ΔJ=0, ±1

13. M + -H 2 para/ortho effects j=0 para 1 j=1, m j =±1 ortho 3 K a =0 weak K a =1 strong Ligand Exchange Preponderance of M + -H 2 (ortho)

14. M + -D 2 para/ortho effects j=0 ortho 2 j =1, m j =±1 para 1 K a =0 weak K a =1 strong Ligand Exchange Both M + -D 2 (para) and M + -D 2 (ortho)

15. Theory vs Experiment - Na + -D 2 K a =0-0 K a =1-1 K a =2-2

16. Infrared spectra of M + -H 2

17. Infrared spectra of M + -D 2

18. 4s 1 3d 1 3D3D 4s 1 3d 2 4F4F 3d 4 5D5D 3d 5 6S6S 4s 1 3d 5 7S7S 4s 1 3d 6 6D6D 3d 8 3F3F 3d 9 2D2D 3d 10 1S1S 4s 1 3d 10 2S2S Transition Metals 2.02 Å 2.32 Å 2.73 Å

19. point charge Separation vs binding energy Poll and Hunt Canadian J. Phys. 63, 84–93 (1985).

20. Transition metals

21. N′ = 7 N′ = 8 2840.0 cm -1 < D 0 < 2856.9 cm -1 Cr + -D 2 Cr + -H 2 D 0 = 2660 ± 175 cm -1 (Bowers) K a = 0 v DD =0 v DD =1 K a = 0 R(7) P(9) N′′ = 9 N′′ = 7 N′ =8 P(8)R(6) N′′ = 6 N′′ = 8 N’= 7

22. Cr + -D 2  DD m  s + n  b

23. Vibrational Band Shifts

24. Olkhov, Nizkorodov, Dopfer JCP 107, 84–93 (1997). Vibrational Band Shifts Vitillo, Damin, Zecchina, Ricchiardi JCP 122, 114311 (2005).

25. Li + -H 2 Na + -H 2 s 0 no hybridization B + -H 2 Zn + -H 2 Mg + -H 2 Al + -H 2 s/p z hybridization Cr + -H 2 d z /s hybridization 2 Vibrational band shifts

26. Electronic Spectra Deeper into the periodic table MW/IR double resonance Measure fragment translational energy Prospects M + -H 2 (v HH =0, J) H 2 (v HH =0,j) + M + D0D0

27. Photoisomerization action spectroscopy Adamson et al., PCCP, 15 pp. 9540 – 9548, 2013

28. Photoactive molecules 11-cis-retinal trans-retinal

29. Ion mobility E Helium buffer gas

30. Ion mobility – a structural tool Von Helden et al. J. Phys. Chem. 1993,97, 8182-8192

31. Ion mobility apparatus

32. electrospray ion source 10 torr He gas V=2000 V Mass range = 100-500 amu t/Δt~60

33. Polymethine dyes DTC DODC HITC λ max = 575 nm λ max = 560 nm λ max = 740 nm

34. DTC laser on/off 0 cm -1 1150 cm -1 1530 cm -1 2 8 9

35. Action spectrum 25 nm λ(nm)

36. Mechanism Collision/RRKM model (Multiwell) C. Rulliere, Chem. Phys. Lett., 43, 303-308, 1976 ΔE d = –(65+0.0058 E) cm -1 2 8 9

37. DODC laser on/off

38. DODC

41. Outlook Biologically significant ions Spectra of cold molecular ions? Triplets? Carbon chains, rings, fullerenes? C7H7+C7H7+

42. Thank you