Molecular Hydrogen attached to Metal Cations Evan Bieske

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

Cl- + 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 $$$

Hydrogen Power

Hydrogen Power

Hydrogen Storage - the bad times

MOFs, zeolites and other junk

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

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

+ M -H j=0 para 1 2 para/ortho effects j=1, mj=± 1 ortho 3 Ka=0 weak Ligand Exchange Preponderance of M+-H 2 (ortho) Ka=1 strong

+ M -D j=0 ortho 2 2 para/ortho effects j =1, mj=± 1 para 1 Ka=0 weak Ligand Exchange Both M+-D 2 (para) and M+-D 2 (ortho) Ka=1 strong

Theory vs Experiment - Na+-D 2 Ka=0 -0 Ka=1 -1 Ka=2 -2

Infrared spectra of + M -H 2

Infrared spectra of + M -D 2

Transition Metals 4 s 13 d 1 3 D 4 s 13 d 2 4 F 3 d 4 3 d 5 5 D 6 S 2. 02 Å 4 s 13 d 5 4 s 13 d 6 7 S 6 D 2. 73 Å 3 d 8 3 d 9 3 d 10 4 s 13 d 10 3 F 2 D 1 S 2 S 2. 32 Å

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

Transition metals

Cr+-D 2 N′ =8 v. DD=1 Ka = 0 N′ = 7 N′ = 8 2840. 0 cm-1 < D 0 < 2856. 9 cm-1 Cr+-H 2 D 0 = 2660 ± 175 cm-1 (Bowers) v. DD=0 Ka = 0 N’= 7 R(7) P(9) R(6) P(8) N′′ = 9 N′′ = 8 N′′ = 7 N′′ = 6

Cr+-D 2 ν DD mν s + nν b

Vibrational Band Shifts

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

Vibrational band shifts Cr+-H 2 Zn+-H 2 B+-H 2 s/pz hybridization dz 2/s hybridization Mg+-H 2 Al+-H Li+-H 2 s 0 no hybridization 2 Na+-H 2

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

Photoisomerization action spectroscopy Adamson et al. , PCCP, 15 pp. 9540 – 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, 8182 -8192

Ion mobility apparatus

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

Polymethine dyes DTC λmax= 560 nm DODC λmax= 575 nm HITC λmax= 740 nm

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

Action spectrum 25 nm λ(nm)

Mechanism 8 2 9 Collision/RRKM model (Multiwell) ΔEd= –(65+0. 0058 E) cm-1 C. Rulliere, Chem. Phys. Lett. , 43, 303 -308, 1976

DODC laser on/off

DODC

DODC

Outlook • Biologically significant ions • Spectra of cold molecular ions? • Triplets? • Carbon chains, rings, fullerenes? C 7 H 7+

Thank you