DeWayne T. Halfen and Lucy M. Ziurys Department of Chemistry

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DeWayne T. Halfen and Lucy M. Ziurys Department of Chemistry
Presentation transcript:

Laboratory Detection and Pure Rotational Spectrum of VCl+ by Velocity Modulation Spectroscopy DeWayne T. Halfen and Lucy M. Ziurys Department of Chemistry Department of Astronomy Steward Observatory Arizona Radio Observatory University of Arizona June 21, 2004

Buy one, get one free VCl+ spectrum appears along with that of VCl Factor of 5 weaker than VCl NO past work on this ion Electronic ground state unknown 4Dr or 4Fr or even 4S First laboratory detection and pure rotational spectrum

Gas-Phase Synthesis of VCl+ Add VCl4 Pressure: 1-2 mTorr 20 mTorr Ar gas also added AC discharge 200 W at 600 W

Use of Velocity Modulation Source Modulation

Energy Level Diagram for VCl+ Ground state unknown VCl: (core) s1d1p2 (X5Dr) VCl+ (core) s1d1p1 ? (X4Fr) (core) s1p2 ? (X4S) (core) d1p2 ? (X4Dr) Four spin components found Vanadium hyperfine I(51V)= 7/2 F = J + I J W 9/2 7/2 5/2 3/2 11/2 J F W J+3/2 J+1/2 J+7/2 J+5/2 J-5/2 J-7/2 J-1/2 J-3/2

W = 3/2 5/2 7/2 9/2 Pattern repeats in V37Cl+

Rotational Spectrum of VCl+ Measured 10 rotational transitions of V35Cl+ Irregular hf pattern in outer two components VCl+ confirmed by VM S/N lower Measured 37Cl isotopomer in natural abundance Velocity Modulation Source Modulation Source Modulation

Spectroscopic Analysis of VCl+ Case (c) analysis W = 5/2 & 7/2 components fit well to half-integer J W = 3/2 & 9/2 don’t fit as well Irregular hyperfine splittings But none fit well to integer J L > 0, not X4S No lambda-doubling observed Only four components X4Fr or X4Dr r0 = 2.1191 Å Effective Spectroscopic Constants for VCl+ W Beff Deff Heff rms 3/2 5364.1363 -0.015742 -3.16E-06 2.535 5/2 5428.3833 0.003359   0.140 7/2 5428.5831 0.003197 0.139 9/2 5487.9555 0.022009 3.17E-06 2.529 aIn MHz

Chloride Neutrals vs. Ions M-Cl bond length shortens from neutral to ion Larger for V vs. Ti Mostly nonbonding 3d electrons Electrostatic attraction increases M+-Cl- vs. M2+-Cl- 4F or 4D

Future Work Finish measurements of VCl+ Determine ground state conclusively Measure spectra of more molecular ions FeCO+ (X4S+) AlNC+ (X2S+)

Acknowledgements Prof. Lucy Ziurys Dr. Aldo Apponi Dr. Chandra Savage Michael Flory Alexandra Janczyk Stefanie Milam Emily Tenenbaum Edward Post NSF NASA