MICROWAVE OBSERVATION OF THE O2-CONTAINING COMPLEX, O2-HCl Frank E. Marshall, Nicole Moon, Thomas D. Persinger, Richard Dawes, and G. S. Grubbs II 72nd International Symposium on Molecular Spectroscopy June 20-24, 2016, Urbana-Champaign, IL, USA; TE04

O2 Complexes Are Rare Making up 21% of our atmosphere, experimental O2 complex studies are quite rare- Stew Novick’s Bibliography1: Ar-O2, DCl-O25, SO2-O2, N2O-O2, and O2-O2 Unfinished work of O2-OCS by Brian Howard2 and H2O-O2 by Endo and coworkers3 HF-O2 by Leopold and coworkers6 and Fawzy and coworkers7 71ST ISMS WA10: CO-O2, Bob McKellar and coworkers 71st ISMS FE09: H2/HD/D2-O2, Paul Raston and Hayley Bunn4 71st ISMS WG14: CO-O2, Grubbs and coworkers Stew Novick. https://wesfiles.wesleyan.edu/home/snovick/SN_webpage/vdw.pdf Brian Howard, Private Communication. Y. Kasai, E. Dupuy, R. Saito, K. Hashimoto, A. Sabu, S. Kondo, Y. Sumiyoshi, and Y. Endo, Atmos. Chem. Phys., 11 (2011), 8607-8612 H. Bunn, T. Bennett, A. Karayilan, and P. Raston, Astrophy. J., 799 (2015) 65. Robert Beaudet, but can only find a link to DOE Summary… S. Wu, G. Sedo, E. M. Grumstrup, K. R. Leopold, J. Chem. Phys., 127 (2007) 204315. W. M. Fawzy, C. M. Lovejoy, D. J. Nesbitt, and J. T. Hougen, J. Chem. Phys., 117 (2002) 693.

Pertinent Previous Work

Experiment CP-FTMW: 2% HCl/10% O2 in Ar, 1.5 atm backing pressure, 5 Hz gas pulse, 5 FIDs/gas pulse, 1 million FIDs, ~20 hrs averaging, 6-12 GHz Used 0.85 atm, 2% HCl in Ar 2 million FIDs for comparison FTMW: Same Gas Mix, Measured possible transitions with Helmholtz coils on and off

CP-FTMW Results

CP-FTMW Results

CP-FTMW Results

FTMW Results

Interpreting Data Real Problem Experiments: continue to do measurements without the Earth’s magnetic field on FTMW First fits of any O2-complex to be achieved in SPFIT/SPCAT

Interpreting Data Real Problem, start with O2-HF Fits with O2-HF have stagnated making O2-HCl assignments a challenge Bringing in Brian Drouin for help with quantum number assignment and interpretation

O2-HCl vs.O2-HF 310 cm-1 wells with 120 cm-1 barrier Semirigid Effective Hamiltonian fit O2-HF S. Wu, G. Sedo, E. M. Grumstrup, and K. R. Leopold. J. Chem. Phys. 127 (2007) 204315.

Additional Goodies Second known measurement of a 38Ar-containing species in natural abundance in microwave!1 Manuscript to be submitted very soon to Chem. Phys. Lett. with Kisiel, Pate, and others. 1. B. L. Cousins, S. C. O’Brien, J. M. Lisy, J. Phys. Chem. 88 (1984) 5142.

Additional Goodies

Acknowledgements GSGII: Missouri S&T Startup; UM Research Board Grant Dawes: NSF  CHE-1300945