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

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Presentation on theme: "DeWayne T. Halfen and Lucy M. Ziurys Department of Chemistry"— Presentation transcript:

1 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

2 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

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

4 Use of Velocity Modulation
Source Modulation

5 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

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

7 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

8 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 = Å Effective Spectroscopic Constants for VCl+ W Beff Deff Heff rms 3/2 -3.16E-06 2.535 5/2 0.140 7/2 0.139 9/2 3.17E-06 2.529 aIn MHz

9 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

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

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

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