1. JET-COOLED LASER SPECTROSCOPY OF A JAHN- TELLER AND PSEUDO JAHN-TELLER ACTIVE MOLECULE: THE NITRATE RADICAL (NO 3 ) 1 Laser Spectroscopy Facility Department of Chemistry The Ohio State University 6/23/2009 2 Arthor Amos Noyes Laboratory of Chemical Physics California Institute of Technology MING-WEI CHEN 1, KANA TAKEMATSU 2, MICHIO OKUMURA 2 and TERRY A. MILLER 1

2.  Introduction  Motivation and aims  Spectroscopy  Geometry and vibronic coupling  Spectroscopic review  Experiment  Apparatus of NO 3 measurement  Initial results of NO 3  Future works  Introduction  Motivation and aims  Spectroscopy  Geometry and vibronic coupling  Spectroscopic review  Experiment  Apparatus of NO 3 measurement  Initial results of NO 3  Future works

3. NO 3 NO 2 N2O5N2O5 -NO 2 -NO 2, h ν +NO 2 hνhν -O O3O3 HNO 3 hydrometeors In troposphere R. P. Wayne et al., Atmos. Envir. 25A, 1 (1991). Nitrate radical (NO 3 ) is an important radical intermediate in the night-time atmosphere, involved in the chemical transformations in both the stratosphere and the troposphere. J.A. Logan, J. Geophys. Res. 86, 7210 (1983). Mixing Ratio 10 -10 10 -11 10 -12 10 -13 10 -14 hνhν NO -O

4. RO 2 RO NONO 2 RO 2 TF08 TF09 TJ08 RD05 RO WJ10 RO 2 OH R’CHO RO RH RO 2 NO 2 RONO 2 HO 2 CO CO 2 R’C(O)O 2 PAN ROOH O2O2 NO 2 HO 2 NO h OH NO 2 NO NO 2 h OH O2O2 O2O2 NO 2 NO  Isomerisation Multistep h NO 2 O 2 RO 2 RO NO 3 NO 2 RO 2 RO NO 3 Day time Night time R. P. Wayne et al., Atmos. Envir. 25A, 1 (1991). Lightfoot et. al. Atmos. Envir. 26A, 1805 (1992). hνhν O3O3

5.  The three energetically lowest states are coupled by vibronic interaction, and therefore a model molecule for understanding the coupling between nearby potential energy surfaces and the Jahn-Teller (JT)/pseudo Jahn-Teller (PJT) effects  Comprehensive understand of the molecular structure with LIF/SEP experiment and benchmark for ab initio calculations of NO 3 M. Okumura J. F. Stanton, A. Deev and J. Sommar, Phys. Scr., 73, C64 (2006).

6. Linear JT Pseudo JT or

7. N O OO D 3h C 2v

8. ............ NO 3 ─ NO 3 + e ─...... MIR NIR LEDF PDS LIF Absorption Vis NO 3 + e ─ T. Ishiwata, I. Tanaka, K. Kawaguchi, and E. Hirota, J. Chem. Phys., 82, 2196 (1985). R. R. Fredl and S. P. Sander, J. Phys. Chem., 91, 2721 (1987). E. Hirota, K. Kawaguchi, T. Ishiwata, and I. Tanaka, J. Chem. Phys., 95, 771 (1991). K. Kawaguchi, T. Ishiwata, I. Tanaka, and E. Hirota, Chem. Phys. Lett., 180, 436 (1991). T. Ishiwata, I. Tanaka, K. Kawaguchi, and E. Hirota, J. Mol. Spec., 183, 167 (1992). E. Hirota, T. Ishiwata, K. Kawaguchi, M. Fujitake, N. Ohashi, and I. Tanaka, J. Chem. Phys., 107, 2829 (1997). K. Kawaguchi, T. Ishiwata, E. Hirota, and I Tanaka, Chem. Phys., 231, 193 (1998). A. Deev, J. Sommar, and M. Okumura, J. Chem. Phys., 122, 224305/1 (2005). M. Jacox and W. E. Thompson, 64 th International Symposium on Molecular Spectroscopy, TF12 (2009). D. A. Ramsay, Proc. Colloq. Spectrosc. Int., 10, 583 (1962). W. J. Marinelli, D. M. Swanson, and H. S. Johnston, J. Chem. Phys., 76, 2864 (1982). M. Jacox and W. E. Thompson, 64 th International Symposium on Molecular Spectroscopy, TF12 (2009). T. Ishiwata, I. Fujiwara, Y. Naruge, K. Obl, and I. Tanaka, J. Chem. Phys., 87, 1349 (1983). B. Kim, P. L. Hunter, and H. S. Johnston, J. Chem. Phys., 96, 4057 (1992). R. T. Carter, K. F. Schmidt, H. Bitto, and J. R. Huber, Chem. Phys. Lett., 257, 297 (1996). L. Valachovic C. Riehn, K. Mikhaylichenko and C. Wittig, Chem. Phys. Lett., 258, 644 (1996). A. Weaver, D. W. Arnold, S. E. Bradforth, and D. M. Neumark, J. Chem. Phys., 94, 170 (1991).

10. Pump Dump T 0 (cm -1 ) 15089 7064 0 ΔE = 8025 cm -1 (Forbidden)

11. LIF SEP P2P2 J. Liu, M.-W. Chen, D. Melnik, J. T. Yi and T. A. Miller, J. Chem. Phys., 130, 074302 (2009)

12. pulse continuous Jet Excitation laser beam N 2 O 5 with He/Ne mixture Dump laser beam Heated nozzle tip

13. L. Valachovic C. Riehn, K. Mikhaylichenko and C. Wittig, Chem. Phys. Lett., 258, 644 (1996). NO 3 LIF spectrum, continuous flow.

14. Moderate-res. a FWHM ~ 0.19(7) cm -1 cw jet, scan step: 0.23 cm -1 pulse jet, scan step: 0.05 cm -1 b R. T. Carter K. F. Schmidt, H. Bitto and J. R. Huber, Chem. Phys. Lett., 257, 297 (1996). High-res. b a L. Valachovic C. Riehn, K. Mikhaylichenko and C. Wittig, Chem. Phys. Lett., 258, 644 (1996).

15.  Summary:  Apparatus with both high-resolution (FWHM~250MHz) and high- accuracy (σ~50MHz) for LIF and SEP measurements.  Preliminary NO 3 LIF of origin band has been obtained.  Future works:  Optimize the system to improve the quality of the LIF spectrum.  Measure the SEP spectra of and transitions.  Summary:  Apparatus with both high-resolution (FWHM~250MHz) and high- accuracy (σ~50MHz) for LIF and SEP measurements.  Preliminary NO 3 LIF of origin band has been obtained.  Future works:  Optimize the system to improve the quality of the LIF spectrum.  Measure the SEP spectra of and transitions....... HR-LIF HR-SEP............ S. Kasahara, K. Kanazawa, Y. Semba, K. Yoshida, M Baba, T. Ishiwata and E. Hirota, 64 th International Symposium on Molecular Spectroscopy, TJ07 (2009).

16. The Miller Group (OSU): Dr. Miller Dmitry Melnik (WJ10, RD05) Phillip Thomas (TJ08) Gabriel Just (TF08, TF09) Rabi Chhantyal-Pun Terrance Codd Neal Klein Funding: NSF Your attention! The Okumura Group (CIT): Dr. Okumura Kana Takematsu (WJ11, RD02)

18. CH 3 ONO (CD 3 ONO) / 1 st run Ne General Valve ControllerDG535 Pulse Generator XeF Excimer Laser XeCl Excimer Laser Ar + Laser Nd:YAG Laser Sirah Dye Laser Pulsed Dye Amplifier PC #1 PC #2 Nozzle Ring Laser T0T0 PMT SHG Frequency reading Photolysis Dump Pump Q-Switch Flash Lamp T 0 / GPIB T0T0 program synchronizing Lens

19. N 2 O 5 / 1 st run Ne General Valve ControllerDG535 Pulse Generator XeCl Excimer Laser Ar + Laser Nd:YAG Laser Sirah Dye Laser Pulsed Dye Amplifier PC #1 PC #2 Nozzle Ring Laser T0T0 PMT Frequency reading Q-Switch Flash Lamp T 0 / GPIB T0T0 program synchronizing Lens Raman cell

20. ...... HR-LIF HR-SEP HR-CRDS............

21. NO 3 NO 2 N2O5N2O5 -NO 2, M -NO 2, h ν +NO 2 hνhν -O O3O3 hydrocarbons Products hydrometeors Products RO 2 /HO 2 /Nitrates OH hydrocarbons NO 3, O 3 HNO 3 hydrometeors NO 3 NO 2 N2O5N2O5 -NO 2, h ν +NO 2 hνhν -O O3O3 hydrocarbons Products HNO 3 aerosol nacreous clouds (polar stratospheric clouds) ClONO 2 HNO 4 HNO 3 hνhν hνhν OH In troposphere In stratosphere R. P. Wayne et al., Atmospheric Environment, 25A, 1 (1991).

22. VOCs R RO 2 RO HO 2 OH HNO 3 ROH + RCHO R’OOR ROOH R’CHO + … NO 3 HNO 3 NO 3 NO 2 O2O2 NO 3 NO 2 O3O3 CO VOCs R. P. Wayne et al., Atmospheric Environment, 25A, 1 (1991). RO 2 TF08 TF09 TJ08 RD05 RO WJ10 NO 3

23. aζ e d 1,2 = −62.24(17)cm -1 1 Y. Endo, S. Saito, and E. Hirota, J. Chem. Phys. 81, 122, (1984) 2 T. Momose, Y. Endo, E. Hirota, and T. Shida, J. Chem. Phys. 88, 5338 (1988) aζ e d = −61.4994(39) cm -1 |N',J',K',p'> |1,3/2,0,-1> |J",P",Σ",p"> |3/2,3/2,1/2,±1> |J,P,Σ,p> |5/2,1/2,-1/2,±1> |3/2,1/2,-1/2,±1> |1/2,1/2,-1/2,±1> |5/2,3/2,1/2,±1> p +1 MW LIF SEP |N',J',K',p'> |1,3/2,0,-1> |J",P",Σ",p"> |3/2,3/2,1/2,±1> |J,P,Σ,p> |5/2,1/2,-1/2,±1> |3/2,1/2,-1/2,±1> |1/2,1/2,-1/2,±1> |5/2,3/2,1/2,±1> |N',J',K',p'> |1,3/2,0,-1> |J",P",Σ",p"> |3/2,3/2,1/2,±1> |J,P,Σ,p> |5/2,1/2,-1/2,±1> |3/2,1/2,-1/2,±1> |1/2,1/2,-1/2,±1> |5/2,3/2,1/2,±1>

24. CH 3 O, 3 2 0 bandCD 3 O, 3 2 0 band

25. CH 3 OCD 3 O

26. ........................ MIR NIR LEDF NO 3 ─ NO 3 + e ─ PDS LIF HR-LIF HR-SEP HR-CRDS............ Absorption Vis

27.  I fl DUMP PUMP s1’s1’ I fl DUMP PUMP s1s1 s0s0  The simple normalization technique works fine except when “dump” laser excites cold band of target molecule. SEP=(S 1 -S 1 ’ ) / S 0 Stimulated Emission Pumping (SEP: Pump-Dump)

28. |N',J',K', P '> → |J,K,Σ, P > D1:|1,1/2,0,-1>→|1/2,1,-1/2,1> D2:|1,3/2,0,-1>→|1/2,1,-1/2,1> D1D2

29. |J',N',K',p'> ← |J'',P'',Σ'',p''> F1:|1/2,1,0,-1>←|3/2,3/2,1/2,1> F2:|3/2,1,0,-1>←|3/2,3/2,1/2,1> F1 F2

30. Ar + Laser CW Ring Dye Laser Computer Etalon Chopper (2KHz) λ/2 PlatePBS PD Calibration System I2I2 50cm ~100mW 1-3 mW Lock- in Experimental Apparatus: Ring Laser & Calibration System LIF resolution (FWHM): ~250MHz LIF accuracy (1σ): ~50MHz to dye amplifier

31. s1s1 s0s0 SEP=s 1 /s 0  I fl DUMP PUMP s1s1 s0s0 SEP=S 1 / S 0 Dump Pump Photolysis Stimulated Emission Pumping (SEP: Pump-Dump)

32. Linear JT Pseudo JT