Bri Gordon Steven T. Shipman New College of Florida

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Presentation transcript:

Bri Gordon Steven T. Shipman New College of Florida Waveguide Chirped-Pulse Fourier Transform Microwave Spectra of 2-Propanethiol Bri Gordon Steven T. Shipman New College of Florida

Astrochemistry of Alkylthiols Few organosulfur compounds have been observed in the ISM. Methanethiol has been observed in Sagittarius B2.* *Linke, R.A.; Frerking, M. A.; Thaddeus, P.; Astrophysical Journal 234, L139 (1979). Larger alkylthiols may be present; existing fits should be extended in order to search for them in the ISM.

Chirped-Pulse Spectrometer 1 Generate pulse Amplify pulse Send pulse to waveguide Amplify molecular emission Record, average emission in the time domain Fourier transform the emission Chirped Pulse (Linear Frequency Sweep) 1) 2) 3) 4) 5), 6)

Senior Thesis Research 1 Worked with three previously studied small alkylthiols. High vapor pressures and strong dipoles: Ethanethiol 1-propanethiol 2-propanethiol g-EtSH 0 cm-1 g'-EtSH 0 cm-1 t-EtSH 213.3 cm-1 1 TG-1-PrSH 0 cm-1 TG’-1-PrSH 0 cm-1 TT-1-PrSH 249.5 cm-1 1 t-2-PrSH 0 cm-1 g-2-PrSH 41.3 cm-1 g’-2-PrSH 41.3 cm-1 DFT B3LYP / 6-311++G(d,p)

Tunneling interactions in EtSH 1 Thiol Potential Energy Scan in EtSH 1 trans gauche' gauche trans The thiol H-atom tunneling through the potential barrier The tunneling induces symmetric and antisymmetric states. c - type transitions between these states are split by as much as 3.5 GHz. Previous* Ab Initio** V2 -135 (27) -152.28 (18) V3 456.4 (20) 451.68 (17) *Nakagawa, J., Kuwada, K., Hayashi, M. Bull. Chem. Soc. Jpn. 49, 3420 (1976). **DFT B3LYP/6-311++G(d,p)

Tunneling interactions in 2-PrSH 1 1 Thiol Potential Energy Scan in 2-PrSH trans gauche' gauche trans b - type transitions between states show tunneling splitting Previous* Ab Initio** V2 - 47.74 (14.4) V3 657.54 489.44 (13.4) *Griffiths, J. H. J. Mol.Spec., 56, 257 (1975). **DFT B3LYP/6-311++G(d,p)

964 peaks above the 3:1 signal to noise threshold 2-Propanethiol 1 (D) trans* µa 1.75 µb 0.004 µc 0.38 µtot 1.80 2 million averages, 7 mTorr, -20° C, 4 μs Fid Experimental Simulated trans Simulated gauche (D) gauche* µa 1.52 µb 0.70 µc µtot 1.81 *DFT B3LYP / 6-311++G(d,p) 964 peaks above the 3:1 signal to noise threshold

964 peaks above the 3:1 signal to noise threshold 2-Propanethiol 1 (D) trans* µa 1.75 µb 0.004 µc 0.38 µtot 1.80 2 million averages, 7 mTorr, -20° C, 4 μs Fid Experimental Simulated trans Simulated gauche (D) gauche* µa 1.52 µb 0.70 µc µtot 1.81 *DFT B3LYP / 6-311++G(d,p) 964 peaks above the 3:1 signal to noise threshold

2-Propanethiol: trans Conformer Expanded View 1 - Experimental - Simulated trans Previous* Current Lines Fit 12 126 Fit RMS (kHz) 50 69 Max J 4 80 # of Lines a – type 78 b – type - c – type 48 *Griffiths, J. H.; J. Mol.Spec., 56, 257 (1975).

2-Propanethiol: gauche Conformer Expanded View 1 Experimental Simulated gauche Previous* Current Lines Fit 55 265 Fit RMS (kHz) 50 112 Max J 5 42 # of Lines Max Splitting (MHz) a – type 96 107.6 b – type 73 1124.6 c – type 91.7 *Griffiths, J. H. ; J. Mol.Spec., 56, 257 (1975).

g-2-PrSH Splitting Transition Frequency (MHz) Splitting (MHz) 7 4 3 ← 7 3 4 (+ -) 22229.60 1050.01 (- +) 23279.61

Results g-2-PrSH Hamiltonian: Ĥ = Ĥ+++ Ĥ-- + Ĥ+- Ĥ++ = A+ Ĵa2 + B+Ĵb2 + C+Ĵc2 Ĥ-- = A–Ĵa2 + B–Ĵb2 + C–Ĵc2 + ∆ν Ĥ+- = Fa (ĴbĴc + ĴcĴb) + Gc (iĴc) + Fc (ĴaĴb + ĴbĴa) gauche trans Ab Initio* Current A (MHz) 7822.81 7873.82 (12) 7831.54 7892.410 (8) B (MHz) 4417.69 4528.44 (11) 4319.54 4414.444 (7) C (MHz) 3106.01 3172.567 (8) 3096.80 3158.072 (7) ∆v (MHz) - 562.259 (21) Fa (MHz) 60.321 (29) Gc (MHz) 8.19 (22) Fc (MHz) 145.33 (132) DJ (kHz) 1.5 1.454 (35) 1.3 1.3 (fixed) DJK (kHz) 2.4 2.344 (62) 2.7 2.61 (12) DK (kHz) 2.6 2.97 (16) 2.77 (33) dJ (kHz) 0.44 0.453 (4) 0.37 0.366 (7) dK (kHz) 3.3 3.390 (47) 2.8 2.997 (92) ФKJ (HZ) 0.0481 (7) Lines Fit 265 126 RMS (kHz) 112 69 Max J 42 80 * DFT B3LYP/6-311++G(d,p)

Conclusions and Future Work 391 (41%) of the 964 peaks have been assigned to the trans and gauche ground state normal species. Next spectra to fit are vibrationally excited states and 34S species

Acknowledgments 1 Professor Shipman Ben Rooks Maria Phillips Christian Metzger Ian Finneran Ben Reinhold New College of Florida The National Science Foundation This material is based upon work supported by the National Science Foundation Division of Chemistry under Grant No.1111101 (co-funded by MPS/CHE and the Division of Astronomical Sciences).

The Galactic Centre and Sagittarius B2, from the European Southern Observatory http://www.eso.org/public/images/eso0924e/

The Galactic Centre and Sagittarius B2, from the European Southern Observatory http://www.eso.org/public/images/eso0924e/

Laboratory improvements: 18-26.5 GHz Spectrometer Our previous frequency range was 8.7 - 18.3 GHz A new circuit was built to extend it to 26.5 GHz (left).

2-Propanethiol 1 2 million averages, 7 mTorr, -20° C, 4 μs Fid 964 peaks above the 3:1 signal to noise threshold