1. New High Precision Linelist of H 3 + James N. Hodges, Adam J. Perry, Charles R. Markus, Paul A. Jenkins II, G. Stephen Kocheril, and Benjamin J. McCall June 16, 2014 - MK06

2. Outline Motivation Instrument Description Previous Work New Lines Future Directions

3. H 3 + Fundamental Benchmark Simplest polyatomic molecule Important for ab initio theory Relativistic, adiabatic and non- adiabatic effects on PES Accuracy of order 300 MHz for low energy Achieved experimental precision! O. L. Polyansky, et al. Phil. Trans. R. Soc. A (2012), 370, 5014-5027. C.M. Lindsay and B.J. McCall. J. Mol. Spectrosc. (2001), 210, 66-83.

4. H 3 + Fundamental Benchmark QED corrections applied to H 3 + Slightly better accuracy Better nonadiabatic corrections are needed Requires higher precision data! O.L. Polyanski et al. Phys. Rev. A (2014) 89, 032505. L.G. Diniz et al. Phys Rev. A (2013) 88, 032506.

5. H 3 + Forbidden Rotational Spectrum Enable quality prediction of forbidden rotational spectrum Predictions are limited to ~600 MHz Measuring fundamental, hot, and overtone bands with precision C.M. Lindsay and B.J. McCall. J. Mol. Spectrosc. (2001), 210, 66-83.

6. H 3 + Astronomical Importance Interstellar medium Deuterium fractionation Located in gas giants’ ionospheres Auroral winds Limited by lab accuracy T. R. Geballe and T. Oka, Nature (1996), 384, 334. P. Drossart et al. Nature (1989), 340, 539. D. Rego et al. Nature (1999), 399, 121. Images From: http://solarsystem.nasa.gov/planets/profile.cfm?Object=Jupiter http://www.ucl.ac.uk/~ucaptss/work/publications/royalsoc/energy.htm

7. Spectroscopic Technique Noise Immune Cavity Enhanced Optical Heterodyne Velocity Modulation Spectroscopy B. M. Siller, et al. Opt. Express (2011), 19, 24822-7. VMS Heterodyne Cavity Enhancement

8. Spectroscopic Technique Noise Immune Cavity Enhanced Optical Heterodyne Velocity Modulation Spectroscopy B. M. Siller, et al. Opt. Express (2011), 19, 24822-7. Ion Selectivity Sensitivity Large Signal NICE-OHVMS

9. Instrumental Layout OPO YDFL EOM Lock-In Amplifier X & Y Signal Lock-In Amplifier X & Y Signal 40 kHz Plasma Frequency 80 MHz 1 × Cavity Free Spectral Range 90 o Phase Shift I P S 2f i  p  s AOM K. N. Crabtree, et al. Chem. Phys. Lett. (2012), 551, 1-6. Ref. Cell Freq. Comb Wave- meter

10. Comb Calibration Wave- meter Freq. Comb AOM […] SignalPump

11. Comb Calibration Wave- meter Freq. Comb AOM […] SignalPump

12. Comb Calibration Wave- meter Freq. Comb AOM […] SignalPump

13. Comb Calibration Wave- meter Freq. Comb AOM […] PumpSignal

14. Production of H 3 + Velocity modulated, l-N 2 cooled, positive column 40 kHz modulation frequency 300-500 mTorr of H 2 High J lines - few Torr of He

15. H 3 + Spectra Doubly Degenerate 2 Band H 3 + Transition Notation

16. Lamb Dips & Saturation High Power  Optical Saturation  Lamb dips In NICE-OHVMS fm-triplet causes many Lamb dips

17. Lamb Dips & Saturation High Power  Optical Saturation  Lamb dips In NICE-OHVMS fm-triplet causes many Lamb dips

18. Lamb Dips & Saturation High Power  Optical Saturation  Lamb dips In NICE-OHVMS fm-triplet causes many Lamb dips

19. Lamb Dips & Saturation High Power  Optical Saturation  Lamb dips In NICE-OHVMS fm-triplet causes many Lamb dips

20. Lamb Dips & Saturation High Power  Optical Saturation  Lamb dips In NICE-OHVMS fm-triplet causes many Lamb dips

21. Lamb Dips & Saturation High Power  Optical Saturation  Lamb dips In NICE-OHVMS fm-triplet causes many Lamb dips

22. Transition Frequencies R(1,0) transition of ν 2 band Lock-In Amplifier X & Y Signal Lock-In Amplifier X & Y Signal Hodges et al. J. Chem. Phys. (2013), 139, 164201. R(2,2) l transition of ν 2 band Relative Frequency (MHz)

23. Last Year’s Transition Freq. TransitionFreq. (MHz) a Shy (MHz) b R(1,1) l 80687424.25(62)80687433.437(250) R(1,0)81720377.29(23)81720371.550(250) R(1,1) u 81730020.44(38)81730028.328(250) R(2,2) l 82804769.99(31)82804761.121(250) R(2,1) l 82908940.58(125) R(2,2) u 84635537.25(54) R(2,1) u 84724846.57(38) R(3,3) l 84839013.46(39)84839021.536(250) R(3,2) l 84907118.76(134) R(4,4) l 86774648.52(39) a. Hodges et al. J. Chem. Phys. (2013), 139, 164201. b. Chen, Peng, Amano, Shy. “Precision Laser Spectroscopy of H 3 + ”. (2013) 68 th ISMS.

24. Some Additional Transition Freq. MoleculeTransitionFreq. (MHz) a Us-Prev. (MHz) HCO + P(5)92145080.8(4) R(3)92947717.3(5) ΔE J=5-3 802636.5(7)-0.6 b CH 5 + ???86880178.469(126)0.25 c a. Hodges et al. J. Chem. Phys. (2013), 139, 164201. b. Cazzoli et al. Astrophys. J., Suppl. Ser. (2012), 203, 11. c. S. Schlemmer. Private Communication, (2013). First Observed Lamb Dip of CH 5 + Hodges et al. J. Chem. Phys. (2013), 139, 164201. HeH + - Adam J. Perry. FA01, 116 RAL, 8:30 am. Relative Frequency (MHz)

25. Transition Freq. TransitionFreq. (MHz) a Schlemmer (MHz) b R(1,1) l 80687424.25(62)80687422.35(30) R(1,0)81720377.29(23)81720376.57(18) R(1,1) u 81730020.44(38)81730019.99(27) R(2,2) l 82804769.99(31)82804770.08(51) R(2,1) l 82908940.58(125) R(2,2) u 84635537.25(54)84635537.15(54) R(2,1) u 84724846.57(38) R(3,3) l 84839013.46(39) R(3,2) l 84907118.76(134) R(4,4) l 86774648.52(39) a. Hodges et al. J. Chem. Phys. (2013), 139, 164201. b. Asvany, Jusko, Schlemmer. Private Communication, (2014).

26. New Transition Freq. TransitionFreq. (MHz)St. Dev. (MHz)St. Err. (MHz)Us-Prev. (MHz) R(4,3) l 86778433.660.760.38208.97 a R(3,1) u 87789812.711.300.5358.30 a R(3,0)87844195.671.220.55118.86 a R(6,6) l 90368280.181.020.51-79.11 b a.T. Oka. Phil Trans R. Soc. London A (1981) 303, 543-549. b.C. M. Lindsay et al. J. Mol. Spectrosc. (2001) 210, 51-59. St. Err. = St. Dev. Of Mean

27. Future Directions Going to continue to measure transitions Want to predict forbidden rotational spectrum Going to need to expand frequency coverage for our instrument

28. Acknowledgements Springborn Fellowship NSF GRF (DGE 11-44245 FLLW)