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June 18, 2007 62 nd Symp. on Molec. Spectrosc. The Pure Rotational Spectra of VN (X 3  r ) and VO (X 4  - ): A Study of the Hyperfine Interactions Michael.

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Presentation on theme: "June 18, 2007 62 nd Symp. on Molec. Spectrosc. The Pure Rotational Spectra of VN (X 3  r ) and VO (X 4  - ): A Study of the Hyperfine Interactions Michael."— Presentation transcript:

1 June 18, 2007 62 nd Symp. on Molec. Spectrosc. The Pure Rotational Spectra of VN (X 3  r ) and VO (X 4  - ): A Study of the Hyperfine Interactions Michael A. Flory and Lucy M. Ziurys Department of Chemistry Steward Observatory University of Arizona

2 June 18, 2007 62 nd Symp. on Molec. Spectrosc. Motivations for High Resolution Vanadium Spectroscopy V-containing compounds frequently being found as air and ground pollutants in Europe, Asia, and South America Astronomy –VO electronic spectrum identified in O-rich stars –VN-type compounds recently detected in comets Understanding of bonding properties Relatively few V radicals studied (VN, VO, VF, VCl, VCl +, VS, VCH) Interesting hyperfine structures from vanadium nuclear spin (I = 7/2)

3 June 18, 2007 62 nd Symp. on Molec. Spectrosc. Radiation Source: Phase- locked Gunn oscillators and Schottky diode multipliers (65- 660 GHz) Gaussian beam optics utilized to minimize radiation loss Reaction Chamber: Double walled, glass cell cooled by methanol with 2 ring electrodes Detector: InSb bolometer Radiation is modulated at 25kHz and detected at 2f Submillimeter Spectroscopy

4 June 18, 2007 62 nd Symp. on Molec. Spectrosc. Most 3d transition metals melt in Broida oven Vanadium not possible using current oven technology (m.p. > 1900 °C) Use new velocity modulation spectrometer Testing reactivity of VCl 4 ( l ) – high v.p. VN: –VCl 4 (1 mTorr) –N 2 (3-5 mTorr) –Ar (20 mTorr) VO: –VCl 4 (1 mTorr) –Residual water –Ar (20 mTorr) 250 W AC discharge Deep purple glow from V emission Molecular Synthesis

5 June 18, 2007 62 nd Symp. on Molec. Spectrosc. VN (X 3  r ) Background Quantum mechanics –S = 1,  = 2 –Hund’s case (a) coupling – R + L + S = J –3 fine structure components (  = 1, 2, 3) –Hyperfine octets from V nucleus (I = 7/2) J J+I=F  = 1  = 3  = 2 Previous work: –Ram et al. have studied many excited states –Balfour et al. (J. Chem. Phys., 1999) examined D 3  – X 3  Both states are perturbed X 3  interacts with 1  state D 3  perturbed by d 1   and e 1  states –Established rotational and fine structure parameters –Determined h 1, h 2, h 3 hyperfine constants

6 June 18, 2007 62 nd Symp. on Molec. Spectrosc. VN Spectra Transitions usually within 20 MHz of frequencies calculated using Balfour et al. Nice Landé pattern Intensity  F F assignment reverse in  = 1 from  = 2, 3 Wide range of h.f. spacing No  -doubling observed No Nitrogen hyperfine (I = 1)

7 June 18, 2007 62 nd Symp. on Molec. Spectrosc. VN Results MHz 7 rotational transitions recorded in range 297 – 528 GHz 157 lines measured

8 June 18, 2007 62 nd Symp. on Molec. Spectrosc. VN Analysis Hund’s case (a) effective Hamiltonian H eff = H rot + H so + H ss + H mhf + H eqQ Only ONE state to fit (X 3  ) Frosch and Foley hf terms fit (a, b, b+c) The  = 2 component is perturbed by 1  Third-order spin-orbit/Fermi contact cross term Manifests as correction to a Included “deperturbation term”,  a = 2a +  a Estimate energy to excited 1  state MHz Present WorkBalfour et al. B18 747.557 4(12)18 746.88(18) D0.027 834 2(36)0.027 29(31) A2 249 700(2 900)2 263 552(29) ADAD -1.53(10)-0.763(27) 188 500(1 100)101 026.6(3.0) D 9.34(13)-0.387(28) H 0.000 296 9(65) a338.80(30) aa 147.32(74) b1 350.8(2.9) b+c1 253.99(55) (b+c) D 0.203(10) eqQ15.9(2.3) h1h1 1 940.3(8.4) h0h0 827.1(6.6) h -1 -586.4(9.0) b+b+ 1 321(83) b-b- 1 404(57) rms0.023138

9 June 18, 2007 62 nd Symp. on Molec. Spectrosc. VO (X 4  - ) Background Quantum mechanics –S = 3/2,  = 0 –Hund’s case (b) coupling – N + S = J –4 fine structure components, closely spaced –Hyperfine octets from V nucleus (I = 7/2) N J+I=F F1F1 F2F2 F3F3 F4F4 N+S=J Previous work: –Many electronic transitions investigated –Richards and Barrow examined internal hyperfine perturbation in X 4  - (1968) –Suenram et al. measured 3 transitions of FTMW spectrum at 8 GHz –Adam et al. combined FTMW with optical data for ground state (1995)

10 June 18, 2007 62 nd Symp. on Molec. Spectrosc. VO (X 4  - ) Spectra Transitions usually within 5-10 MHz of frequencies calculated using Adam et al. NO traditional patterns for V octets Dramatically varying widths in h.f. spacing Form “band-heads” Internal hyperfine perturbation to F 2 and F 3  N = 0,  J = 1,  F = 0 –Basis set breaks down and quantum numbers difficult to assign in Hamiltonian F 1 and F 4 due to matrix elements –No difficulty in assigning or fitting transitions F4F4 F3F3 F2F2 F1F1

11 June 18, 2007 62 nd Symp. on Molec. Spectrosc. VO (X 4  - ) Results MHz F 4 (J″ = N″ – 3/2) b F 3 (J″ = N″ – 1/2) F 2 (J″ = N″ + 1/2) N′ F′  N″F″ obs-calc F′  F″ obs-calc F′  F″ obs-calc 9483 291860.8010.172 54 293722.7450.024 65 296266.224-0.070 54 291780.8590.030 65 293739.109-0.011 76 296245.767-0.041 65 291716.2820.035 76 293750.243-0.007 87 296225.376-0.026 76 291666.6590.066 87 293755.008-0.031 98 296206.913-0.007 87 291631.4830.028 98 293752.100-0.018 109 296193.3780.026 98 291610.3490.039 109 293739.1090.023 1110 296190.7510.134 109 291602.5840.058 1110 293710.7520.028 1211 296212.942-0.027 1110 291607.4190.025 1211 293653.6300.054 1312 296305.960-0.040 10594 325054.6430.038 65 326577.527-0.005 76 328762.810-0.003 65 324991.9380.000 76 326606.107-0.046 87 328730.692-0.052 76 324942.315-0.003 87 326629.529-0.048 98 328700.2030.018 87 324905.508-0.009 98 326646.815-0.039 109 328672.780-0.020 98 324881.189-0.040 109 326656.7530.059 1110 328651.530-0.034 109 324868.951-0.136 a 1110 326656.6530.074 1211 328643.093-0.043 1110 324868.7510.096 1211 326640.4050.024 1312 328666.370-0.024 1211 324879.4380.006 1312 326589.8270.003 1413 328802.908-0.041 7 rotational transitions recorded in range 291 – 525 GHz

12 June 18, 2007 62 nd Symp. on Molec. Spectrosc. VO MHzMM-waveAdam et al. B16 379.618 6(14)16 379.798(17) D0.019 363 8(39)0.019 460 0(96)  672.168(39)672.328(42) DD 0.001 970(75)0.001 80(68) ss 0.220 4(81)0.243(95) 60 881.03(55)60 884.97(45) D 0.018 16(61)0.011 5(48) bFbF 778.737(66)777.54(15) c-129.84(19)-134.83(46) cIcI 0.192 8(51) bsbs -0.660(14)-0.472(37) eqQ-2.5(1.3)40.17(48) rms0.05211 VO Analysis Combined sub-mm with FTMW data Hund’s case (b) effective Hamiltonian H eff = H rot + H ss + H mhf + H eqQ Higher order terms required –b s = Third-order spin-orbit distortion to Fermi contact when S > 1 –  s = Third-order spin-rotation Generally good agreement with previous values Better predictions of sub-millimeter frequencies

13 June 18, 2007 62 nd Symp. on Molec. Spectrosc. Conclusions Measured pure rotational spectra of VO and VN Established global fit of hyperfine constants in VN ground state Both radicals exhibit interesting perturbations to the hyperfine structure VCl 4 is a possible V source for additional radical synthesis in the future (VC, VNC, VOH, …)

14 June 18, 2007 62 nd Symp. on Molec. Spectrosc. Thanks to…  Lucy Ziurys  Ziurys Group  Dr. Aldo Apponi  Dr. DeWayne Halfen  Stefanie Milam, Emmy Tenenbaum, Robin Pulliam, Ming Sun  Funding  NSF  NASA Laboratory Astrophysics

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