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

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 + +

Hydrogen Power

Hydrogen Storage - the bad times

MOFs, zeolites and other junk

Gas Phase Binding Enthalpies Bowers, Kemper, Bushnell ( )

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 cm cm -1 ΔK a =0 ΔJ=0, ±1

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)

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)

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

Infrared spectra of M + -H 2

Infrared spectra of M + -D 2

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

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

Transition metals

N′ = 7 N′ = cm -1 < D 0 < 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

Cr + -D 2  DD m  s + n  b

Vibrational Band Shifts

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

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

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

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

Photoactive molecules 11-cis-retinal trans-retinal

Ion mobility E Helium buffer gas

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

Ion mobility apparatus

electrospray ion source 10 torr He gas V=2000 V Mass range = amu t/Δt~60

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

DTC laser on/off 0 cm cm cm

Action spectrum 25 nm λ(nm)

Mechanism Collision/RRKM model (Multiwell) C. Rulliere, Chem. Phys. Lett., 43, , 1976 ΔE d = –( E) cm

DODC laser on/off

DODC

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

Thank you