63rd Symposium on Molecular Spectroscopy June 18, 2008 Submillimeter Spectroscopy of ZnO (X 1  + ) Lindsay N. Zack Robin L. Pulliam Lucy M. Ziurys Departments.

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Presentation transcript:

63rd Symposium on Molecular Spectroscopy June 18, 2008 Submillimeter Spectroscopy of ZnO (X 1  + ) Lindsay N. Zack Robin L. Pulliam Lucy M. Ziurys Departments of Chemistry and Astronomy Steward Observatory University of Arizona

63rd Symposium on Molecular Spectroscopy June 18, 2008 Previous Work Recent high-resolution spectroscopic studies of zinc molecules: ZnF (Flory et al. 2006), ZnCl (Tenenbaum et al. 2007), HZnCl (WF15), HZnCN (WF16) All diatomic 3d transition metal oxides have been studied with high-resolution spectroscopy, except ZnO (Merer 1989) Most previous studies of ZnO have focused on its bulk properties- dielectric constant and bandgap energy have been determined (eg. Singh 2007) PES (Moravec 2001; Fancher 1998) and FTIR (matrix) (Chertihin 1996) have been used to determine the equilibrium bond lengths and vibrational frequencies Several theoretical studies predict r e = Å (eg. Boldyrev and Simons 1997; Bridgeman and Rothery 2000)

63rd Symposium on Molecular Spectroscopy June 18, 2008 Submillimeter Spectroscopy Radiation Source: Phase- locked Gunn oscillators and Schottky diode multipliers ( GHz) Gaussian beam optics Reaction Chamber: Water- cooled steel cell containing a Broida-type oven Detector: InSb bolometer

63rd Symposium on Molecular Spectroscopy June 18, 2008 Gas-Phase Synthesis of ZnO Zn vapor produced in Broida- type oven –m.p. 420  C –Zn would coat optics if not melted slowly ~ 4 mTorr N 2 O d.c. discharge needed mTorr Ar carrier gas Initial search ~ 100 GHz (~7B)

63rd Symposium on Molecular Spectroscopy June 18, ZnO J = v = 0

63rd Symposium on Molecular Spectroscopy June 18, 2008 Five Isotopologues

63rd Symposium on Molecular Spectroscopy June 18, 2008 ZnO (X 1  + ) J =

63rd Symposium on Molecular Spectroscopy June 18, 2008 J = ZnO v = 0 66 ZnO v = 0 67 ZnO v = 0 68 ZnO v = 0 70 ZnO v = 0 5 isotopologues 64 ZnO : 66 ZnO : 67 ZnO : 68 ZnO : 70 ZnO 49 : 28 : 4 : 19 : 0.6%

63rd Symposium on Molecular Spectroscopy June 18, 2008 J = ZnO v = 0 66 ZnO v = 0 67 ZnO v = 0 68 ZnO v = 0 70 ZnO v = 0 67 ZnO v = 1 68 ZnO v = 1 66 ZnO v = 1 64 ZnO v = 1

63rd Symposium on Molecular Spectroscopy June 18, ZnO v = 2 67 ZnO v = 2 64 ZnO v = 3 66 ZnO v = 2 68 ZnO v = 2 66 ZnO v = 3 68 ZnO v = 3 6 nO v = 4 Up to v = 4 J = 16 – 17 Up to v = 4 64 ZnO v = 0 66 ZnO v = 0 67 ZnO v = 0 68 ZnO v = 0 70 ZnO v = 0 67 ZnO v = 1 66 ZnO v = 2 66 ZnO v = 1 64 ZnO v = 1

63rd Symposium on Molecular Spectroscopy June 18, 2008 Transition Frequencies (in MHz) 116 lines were measured for 5 isotopologues over GHz

63rd Symposium on Molecular Spectroscopy June 18, 2008 Ground State Constants (in MHz) 64 ZnO 66 ZnO 67 ZnO 68 ZnO 70 ZnO B0B (62) (62) (62) (62) (62) D0D (11) (11) (11) (11) (11) rms For 64 ZnO, B 0 = MHz and D 0 = MHz Very low rms!

63rd Symposium on Molecular Spectroscopy June 18, 2008 Equilibrium Parameters 64 ZnO 66 ZnO 67 ZnO 68 ZnO B e (MHz) (66) (66) (84) (66)  e (MHz) (29) (30) (66) (30) D e (MHz) (12) (12) (15) (12)  e (MHz) (50) (50) (11) (50) r e (Å) (43) (43) (44) (44)  e (cm -1 ) (20)730.50(20)729.43(20)728.39(20)  e x e (cm -1 ) (18)4.8401(18)4.8271(19)4.8160(19) D E, v =0 (eV)3.3720(23) (23)3.3694(23)

63rd Symposium on Molecular Spectroscopy June 18, d Transition Metal Sulfide and Oxide Bond Lengths Oxide series now complete ZnO ( 1  + )  4  4  2  2  4 ??

63rd Symposium on Molecular Spectroscopy June 18, 2008 Summary and Future Work The predicted 1  + ground state of ZnO was confirmed The 3d transition metal oxide series has been completed Study ZnS to complete sulfide series and compare trends between oxides and sulfides FTMW study of 67 ZnO to determine quadrupole hyperfine structure Astronomical search in oxygen-rich environment?

63rd Symposium on Molecular Spectroscopy June 18, 2008 Acknowledgements Professor Lucy Ziurys Robin Pulliam Dr. DeWayne Halfen Ming Sun, Emmy Tenenbaum, Jessica Dodd, and Gilles Adande Funding- NSF and NASA