CAVITY AND CHIRPED PULSE ROTATIONAL SPECTRUM OF THE LASER ABLATION SYNTHESIZED, OPEN-SHELL MOLECULE TIN MONOCHLORIDE, SnCl G. S. GRUBBS II, DANIEL J. FROHMAN,

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CAVITY AND CHIRPED PULSE ROTATIONAL SPECTRUM OF THE LASER ABLATION SYNTHESIZED, OPEN-SHELL MOLECULE TIN MONOCHLORIDE, SnCl G. S. GRUBBS II, DANIEL J. FROHMAN, STEWART E. NOVICK Wesleyan University, Middletown, CT, USA S. A. COOKE University of North Texas, Denton, TX,USA

Complexities Isotopes Nuclear Spin Electronic Spin 10 isotopes of Tin 2 isotopes of Chlorine Nuclear Spin Chlorine I = 1.5 Some Tin I = 0.5 Electronic Spin 2Πr ground state Species Abundance Nuclear Spin 112Sn 0.97 % 114Sn 0.66 % 115Sn 0.34 % 0.5 116Sn 14.54 % 117Sn 7.68 % 118Sn 24.22 % 119Sn 8.59 % 120Sn 32.58 % 122Sn 4.63 % 124Sn 5.79 % 35Cl 75.78 % 1.5 37Cl

Hund’s Cases Case c Case a C.H. Townes and A.L. Schawlow, Microwave Spectroscopy (Dover Publications, Inc., New York, 1975)

What is considered “heavy”, or, rather, when do we start to move into case c?

In Conjunction

Walker-Gerry Ablation Nozzle Similar to Smalley Nozzle

2, -1, 3/2, 3← 1, 1, 1/2, 2; e parity Cavity Measurement: Sample Spectrum 2, -1, 3/2, 3← 1, 1, 1/2, 2; e parity Cavity Measurement: 10147.1840 MHz 2, -1,3/2, 3← 1, 1, 1/2, 2; e parity Chirp Measurement: 10147.1873 MHz

Manifestation of Complexity Λ-doubling 120Sn35Cl Λ-doubling 118Sn35Cl Manmade; Ar-Cl2 Complex Others: Magnetic Hyperfine- Cl Nuclear Quadrupole Coupling- Cl Magnetic Coupling- Tin UP TO 20 ISOTOPOLOGUES!!!!

120Sn35Cl (2Π1/2,v=0) Parameters Literature1 Chirp Fit B0 /MHz 3352.6 (4) 3345.545(1) D0 /kHz 1.34 (4) 1.32(8) p0 /MHz -268.(8) -256.366(3) A0 /MHz 70704900 (900) 70704941.99 (held) AD_0 /MHz 6.9 (1) 6.895 (held) a /MHz --------- 33.534(3) d /MHz 13.895(3) eQq1(Cl) /MHz -25.01(1) RMS /kHz 4.96 Attributed Uncertainty of 15 kHz given to all CP-FTMW measurements 1. N. Badowski, W. Zyrnicki, and J. Borkowska-Burnecka, J. Phys. B: At. Mol. Phys., 20 (1987) 531.

Energy Levels of 120Sn35Cl ~770 MHz p ~ -260 MHz Split=-p(J+0.5)

Chirp Fits Parameter 120Sn35Cl 118Sn35Cl 116Sn35Cl 120Sn37Cl B0 /MHz 3345.545(1) 3358.335(2) 3371.561(2) 3205.9094(9) D0 /kHz 1.32(8) 1.3(1) 1.3(2) 0.99(7) p0 /MHz -256.366(3) -257.36(4) -258.38(5) -245.587(2) A0 /MHz 70704941.991 AD_0 /MHz 6.8951 a /MHz 33.534(3) 33.535(5) 33.526(7) 27.912(3) d /MHz 13.895(3) 13.898(4) 13.889(7) 11.571(3) eQq1(Cl) /MHz -25.01(1) -25.00(2) -25.02(3) -19.72(1) RMS2 /kHz 4.96 7.51 6.06 2.17 Attributed Uncertainty of 15 kHz given to all CP-FTMW measurements 1Held to the Literature Values

Zeeman Splitting 2, -1, 3/2, 3← 1, 1, 1/2, 2 For a Free Electron: W. Gordy and R. L Cook, Microwave Molecular Spectra: Techniques in Chemistry Vol. XVIII, Wiley, New York, 1984. For a Free Electron: gs = 2.0023 RA08 66th Ohio State Conference For a 2Π1/2, Λ = 1, Σ =1/2 gJ ≅ 0 (less than 1 kHz) We expect no splitting! With Earth’s Magnetic Field ~1/2 Gauss Bucking the Earth’s Magnetic Field The slight Zeeman splitting ⇓ NOT pure case a 1

Chirp/Cavity Comparison Parameter 120Sn35Cl Chirp 120Sn35Cl Cavity B0 /MHz 3345.545(1) D0 /kHz 1.32(8) 1.38(9) p0 /MHz -256.366(3) -256.368(3) A0 /MHz 70704941.991 AD_0 /MHz 6.8951 a /MHz 33.534(3) 33.536(3) d /MHz 13.895(3) 13.898(2) eQq1(Cl) /MHz -25.01(1) -25.00(1) Number of Lines 22 17 RMS /kHz 4.96 3.82

Magnetic Hyperfine Species a d Reference 12C35Cl 80.199(54) 82.212(37) 28Si35Cl 43.67(39) 46.40(94) 2 74Ge35Cl Not Determined 3 120Sn35Cl 33.534(3) 13.895(3) This Work 208Pb35Cl 30.17(4) -40.83(4) 4 Y. Endo, S. Saito, and E. Hirota, J. Mol. Spectr., 94 (1982) 199. M. Tanimoto and S. Saito, Y. Endo, and E. Hirota, J. Mol. Spectr., 103 (1984) 330. K. Tanaka, H. Honjou, M. Tsuchiya, and T. Tanaka, J. Mol. Spectr., 251 (2008) 369. C. T. Dewberry, G. S. Grubbs II, K. C. Etchison, and S. A. Cooke. 65th Ohio State University International Symposium, RC07.

Comparisons of eQq1 Species eQq1 value Reference 12C35Cl -34.26(13) 1 28Si35Cl -23.13(96) 2 74Ge35Cl Not Reported 3 120Sn35Cl -25.01(1) This Work 208Pb35Cl -24.9(1) 4 Y. Endo, S. Saito, and E. Hirota, J. Mol. Spectr., 94 (1982) 199. M. Tanimoto and S. Saito, Y. Endo, and E. Hirota, J. Mol. Spectr., 103 (1984) 330. K. Tanaka, H. Honjou, M. Tsuchiya, and T. Tanaka, J. Mol. Spectr., 251 (2008) 369. C. T. Dewberry, G. S. Grubbs II, K. C. Etchison, and S. A. Cooke. 65th Ohio State University International Symposium, RC07.

Conclusions 4 isotopologues have been fit with the chirped pulse data and 1 isotopologue with the cavity Λ – doubling observed and explained Nuclear Magnetic and Quadrupole Coupling data compare well with the literature trends of other tetrel chlorides Zeeman splitting suggests not purely Hund’s case a

Acknowledgements NSF CHE-1011214 for Wesleyan NSF and DOE for University of North Texas