June 16-20, 2008 63 rd International Symposium on Molecular Spectroscopy Direct Measurements of the Fundamental Rotational Transitions of CD and 13 CH.

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Presentation transcript:

June 16-20, rd International Symposium on Molecular Spectroscopy Direct Measurements of the Fundamental Rotational Transitions of CD and 13 CH (X 2 Π r ) D. T. Halfen, L. M. Ziurys Dept. of Chemistry Dept. of Astronomy Steward Observatory University of Arizona J.C. Pearson, and B.J. Drouin Jet Propulsion Laboratory California Institute of Technology

June 16-20, rd International Symposium on Molecular Spectroscopy Importance of CH in Astrophysics CH observed in many interstellar environments Tracer of Diffuse Gas at UV, optical wavelengths  One of original four interstellar species  Detected via electronic spectra Observed optically in Comets Also found towards many Denser Clouds  studied via lambda-doubling transition in J = ½ level ( 3 hyperfine components)  limited observations of rotational transitions in Far-IR (Kuiper Airborne Observatory) CH: F-X Band: X Per CH: Hale-Bopp CH at 3 GHz: hf components of Lambda-doublet

June 16-20, rd International Symposium on Molecular Spectroscopy Importance of CD and 13 CH CH in many interstellar environments Fundamental building block of interstellar carbon chemistry Useful to measure 12 C/ 13 C ratios via 13 CH/ 12 CH  tracer of Galactic Chemical Evolution D/H ratio also significant  indicator of fractionation  follow chemical pathways Effective avenue to measure such ratios  Observing rotational spectra  Become very feasible with Herschel, SOFIA KAO CH spectrum Herschel Space Observatory

June 16-20, rd International Symposium on Molecular Spectroscopy Energy Level Diagram: case (b) CD: Brown and Evenson (1989) Wienkoop et al. (2003)  LMR, FTIR measurements  in mid, far IR 13 CH: Davidson et al (2004)  LMR of rotational transitions McCarthy et al. (2006)  FTMW measurements of several lambda-doublets with hf This work: measure rotational transitions directly CD and 13 CH: N = 1→1 CD: N = 1 →2 Past Rotational Spectroscopy

June 16-20, rd International Symposium on Molecular Spectroscopy T R * (K) Frequency (GHz) SO 2 CH 3 OH HOOCH 3 U CH 3 OCH 3 CH 3 CH 2 CN NH 2 CHO U CH 2 CHCN U U U U CH 3 OCH 3 U U HCOOH & CH 3 CH 2 CN Are such measurements necessary ?? SgrB2(N)

June 16-20, rd International Symposium on Molecular Spectroscopy Millimeter Direct Absorption with AC Longitudinal Discharge

June 16-20, rd International Symposium on Molecular Spectroscopy JPL Instrumental Details Source developments thanks to Herschel/HIFI Direct Absorption, DC discharge

June 16-20, rd International Symposium on Molecular Spectroscopy Detector Gas Cell Reactant Radiation Source Arizona System

June 16-20, rd International Symposium on Molecular Spectroscopy Gas-Phase Production of CD and 13 CH Arizona Studies Precursor gas: CD 4 or 13 CH 4 –Pressure: 1-5 mTorr Carrier Gas: 40 mTorr Argon AC discharge for –200 W at 600  –Pink-purple glow JPL CD synthesis - 5 mTorr CH 4 /20 mTorr D 2 with 100 mTorr He - DC discharge

June 16-20, rd International Symposium on Molecular Spectroscopy Arizona Data JPL Data Hyperfine Structure Resolved in N = 1→1 Spectrum Halfen et al Ap.J., in press

June 16-20, rd International Symposium on Molecular Spectroscopy Resolved 13 C and H hf structure Arizona Data

June 16-20, rd International Symposium on Molecular Spectroscopy Observed Transition Frequencies of CD (X 2  r ) N  NN J  JJ F  FF Parity obs (MHz) obs -  calc (MHz) 1  11.5   +   a  1.5+   a  +   a  0.5+   a  11.5   1.5       0.5       11.5  0.5  1.5   a    a  2.5   a    a  0.5   a  1.5   a    a  11.5  2.5  +    12.5   2.5   a  1.5   a  12.5   2.5+   a  1.5+   a a Blended lines. CD

June 16-20, rd International Symposium on Molecular Spectroscopy Observed Transition Frequencies of 13 CH (X 2  r ) a N  NN J  JJ F1F1  F1F1 F  FF Parity obs (MHz) obs -  calc (MHz) 1  11.5   1  1.5+    11.5  +    10.5  +    11.5  0.5+    11.5  +    12.5  1.5+    11.5  0.5+    00.5  +    01.5  0.5+    11.5   01.5  0.5    00.5     11.5     10.5  1.5    10.5     12.5  1.5    11.5     11.5  0.5   a Coupling scheme: J = N + S; F 1 = J + I 1 ; F = F 1 + I 2 ; where I 1 and I 2 are the 13 C and H nuclear spins, respectively. 13 CH

June 16-20, rd International Symposium on Molecular Spectroscopy Spectroscopic Constants for CD (X 2  r ) ParameterThis work (MHz)Wienkoop et al. ( MHz) B (80) (13) D12.698(90) (36) H c A c (90)  (91) (23) p544.89(27)544.41(57) pDpD c (39) q (97)339.45(18) qDqD (34) (69) a (D)8.74(27)8.05(99) b F (D)-8.797(72)-8.99(87) c (D)9.26(81)8.9(1.6) d (D)7.054(87)7.06(90) eqQ(D)-0.69(41) - C Held fixed. Deuterium eqQ determined Improved D hf constants Improved fine structure constants Good agreement with past work

June 16-20, rd International Symposium on Molecular Spectroscopy Spectroscopic Constants for 13 CH (X 2  r ) a ParameterThis work (MHz)McCarthy et al. (MHz)Davidson et al. (MHz) B (18) (270) (285) D a (150) (144) A a (1.14) (1.23)  a (33) (36) p (53)998.12(48)998.39(72) pDpD a (54)-0.305(69) q (10) (81) (132) qDqD d (78) (117) a ( 13 C) (85)218.20(57)218.10(1.26) b F ( 13 C)41.989(91)41.83(90)41.99(84) c ( 13 C) (19) (1.17)-131.0(3.6) d ( 13 C)276.67(16)275.14(1.20)275.54(78) d D ( 13 C)-0.393(24)-0.166(177) a (H)54.410(88) (39) a b F (H)-57.60(10) a a c (H)57.19(23) a a d (H)43.841(41)43.836(54) a d D (H)0.0836(50)0.0826(78) a Held fixed. Proton b F and c established Improved 13 C hyperfine and lambda-doubling constants 4 MHz discrepancy in B

June 16-20, rd International Symposium on Molecular Spectroscopy In Conclusion Lowest energy rotational transitions of CD and 13 CH measured Precision of kHz Determination of hyperfine parameters (eqQ(D), b F (H), c(H)) Improvement of other spectroscopic constants Important for upcoming Herschel, SOFIA observations Used to establish 12 C/ 13 C ratios Degree of deuterium enhancement in fundamental building block CH ACKNOWLEDGEMENTS: NASA Lab Astrophysics Program