Infrared Spectroscopic Studies of OCS Trapped in Solid Parahydrogen: Indirect Evidence of Large Amplitude Motions Morgan E. Balabanoff and David T. Anderson.

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Infrared Spectroscopic Studies of OCS Trapped in Solid Parahydrogen: Indirect Evidence of Large Amplitude Motions Morgan E. Balabanoff and David T. Anderson Department of Chemistry, University of Wyoming Laramie, WY 82071-3838 danderso@uwyo.edu This research is sponsored in part by the Chemistry Division of the National Science Foundation (CHE 13-62497). Paper: TF02, 1:47 to 2:02 pm TF. Mini-Symposium: Spectroscopy of Large Amplitude Motions

Carbonyl sulfide (OCS) – Infrared chromophore n3 CO stretch (2062 cm-1) n2 bend (520 cm-1) n1 CS stretch (859 cm-1) B = 0.20286 cm-1 TF02: SPEC LAMs David T. Anderson University of Wyoming

Previous studies of OCS(H2)N clusters Superfluid helium droplets Supersonic expansion T = 0.15 – 0.37 K T ≤ 1 K Droplets: S. Grebenev, B. Sartakov, J. P. Toennies, A. Vilesov, Science 289, 1532 (2000). Beams: J. Tang and A.R.W. McKellar, J. Chem. Phys. 116, 646 (2002). TF02: SPEC LAMs David T. Anderson University of Wyoming

Vibrational frequency reflects cluster size and “structure” hnIR hnIR hnIR hnIR v=0 v=0 v=0 v=0 monomer N=1 N=2 N=3 TF02: SPEC LAMs David T. Anderson University of Wyoming

Infrared spectroscopic measurements of clusters formed in seeded jets He ortho-H2 para-H2 J. Tang and A.R.W. McKellar, J. Chem. Phys. 116, 646 (2002). J. Tang, Y. Xu, A.R.W. McKellar, W. Jäger, Science 297, 2030 (2002). J. Tang and A.R.W. McKellar, J. Chem. Phys. 121, 3087 (2004). TF02: SPEC LAMs David T. Anderson University of Wyoming

N=5 cluster is special: trend breaker TF02: SPEC LAMs David T. Anderson University of Wyoming

Synthesis of parahydrogen (p-H2) enriched crystals n-H2 cold tip 2000 ppm Fe(OH)3 100 ppm p-H2 infrared beam TF02: SPEC LAMs David T. Anderson University of Wyoming

Infrared spectrum of OCS in solid pH2 (CO stretch region) [OCS]= 1 ppm [o-H2]= 100 ppm T = 1.89 K as-deposited 2055.51 cm-1 matrix shift = -6.69 cm-1 OC32S gas-phase n0 = 2062.2013 cm-1 TF02: SPEC LAMs David T. Anderson University of Wyoming

Fine structure not just sulphur isotopomers OC32S ? OC34S ? OC33S TF02: SPEC LAMs David T. Anderson University of Wyoming

“Simpler” spectrum at “high” temperature OC32S OC34S 4.80 K 1.70 K TF02: SPEC LAMs David T. Anderson University of Wyoming

Some peaks show a strange temperature dependence * * TF02: SPEC LAMs David T. Anderson University of Wyoming

H2-OCS intermolecular PES; doughnut model F. Paesani and K.B. Whaley, Mol. Phys. 104, 61-72 (2006). TF02: SPEC LAMs David T. Anderson University of Wyoming

Nitrous Oxide (N2O) – OCS mimic n3 NN stretch (2223.8 cm-1) n2 bend (588.8 cm-1) n1 NO stretch (1284.9 cm-1) B = 0.4190 cm-1 TF02: SPEC LAMs David T. Anderson University of Wyoming

H2-N2O intermolecular PES – 6D, 4D, 2D L. Wang, D. Xie, R.J. Le Roy, W-P Deng, P-N. Roy, J. Chem. Phys. 139, 034312 (2002). TF02: SPEC LAMs David T. Anderson University of Wyoming

Does N2O “fit” in a single substitution site? S-M. Hu, L. Wan, J-H. Du, G. Xu, W-P. Deng, L. Wu, S-X. Tian, Y. Chen, Vib. Spec. 50, 36 (2009). TF02: SPEC LAMs David T. Anderson University of Wyoming

Let’s look at this further, does N2O fit? Y X Z TF02: SPEC LAMs David T. Anderson University of Wyoming

6 minima for N2O in single substitution hcp Y 5 6 theta X Z 3 4 phi 2 Theta phi Vmin(q,f) cm-1 90 50 -781.49 90 125 -781.49 45 215 -781.35 135 215 -781.35 45 325 -781.35 135 325 -781.35 1 146 pH2 molecules fixed N2O com fixed TF02: SPEC LAMs David T. Anderson University of Wyoming

Can we form particle(s) on a ring? Y theta X Z phi N=5 TF02: SPEC LAMs David T. Anderson University of Wyoming

Summary Is it possible for impurities to induce delocalized motions in the surrounding pH2 solvation shell? Can these different solvation geometries be detected using FTIR spectroscopy and modeling? Anomalies in the IR spectra of OCS and N2O still need to be explored further Quantum solvation in solid pH2 is a delicate balance between zero point energy and potential energy – can lead to counterintuitive effects! TF02: SPEC LAMs David T. Anderson University of Wyoming

The people who do the work and funding Morgan E. Balabanoff Aaron I. Strom Wyoming Research Scholar Fredrick M. Mutunga This research is sponsored in part by the Chemistry Division of the US National Science Foundation through grant (CHE-13-62497). We would also like to acknowledge funds from the UW Research Office for the helium recovery system. TF02: SPEC LAMs David T. Anderson University of Wyoming

12 minima for N2O in single substitution hcp Y theta X Z phi Theta phi Vmin 40 0 -806.15 140 0 -806.15 65 45 -805.17 115 45 -805.17 65 315 -805.02 115 315 -805.02 146 pH2 molecules fixed N2O com relaxed

Vibrational shifts reflect structure - gas phase - this work

Calculated “structures” for OCS(p-H2)N monomer N = 1 N = 2 N = 3 N = 4 N = 5 N = 6 N = 7 F. Paesani, R. E. Zillich, and K. B. Whaley, J. Chem. Phys. 119, 11682 (2003).

Vibrational frequency reflects cluster size and structure hnIR hnIR hnIR hnIR v=0 v=0 v=0 v=0 monomer N=1 N=2 N=3

Cluster distribution shifts with temperature high temperature OCS ↔ OCS(o-H2) ↔ OCS(o-H2)2 ↔ OCS(o-H2)3

Cluster distribution shifts with temperature Low temperature OCS ↔ OCS(o-H2) ↔ OCS(o-H2)2 ↔ OCS(o-H2)3

Ortho-H2 molecules cluster around OCS [OCS] = 1 ppm [o-H2] = 100 ppm T = 1.70 K annealed 1 2 3 5 4 7 6 8