1 TORSION-ROTATION-VIBRATION EFFECTS IN THE v 20, 2 v 21, 2 v 13 AND v 21 + v 13 STATES OF CH 3 CH 2 CN Adam M. Daly, John C. Pearson, Shanshan Yu, Brian J. Drouin, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA; Celina Bermúdez, José Luis Alonso, Grupo de Espectroscopia Molecular, Laboratorio de Espectroscopia y Bioespectroscopia, Unidad Asociada CSIC, Universidad de Valladolid, Valladolid, España 6/19/2014RA 04

2 Background 6/19/2014RA 04 Recent Spectroscopic work presented here WH13 (2009) SUBMILLIMETER SPECTROSCOPY OF THE OUT-OF-PLANE BENDING STATE v 20 OF C 2 H 5 CN.JOHN C. PEARSON, CAROLYN S. BRAUER, SHANSHAN YU AND BRIAN J. DROUIN, JET PROPULSION LABORATORY, CALIFORNIA INSTITUTE OF TECHNOLOGY, 4800 OAK GROVE DR., PASADENA, CA TC 07 (2009) ANALYSIS OF THE LOWEST IN-PLANE BEND AND FIRST EXCITED TORSIONAL (v 13 and v 21 ) STATE OF CH 3 CH 2 CN. CAROLYN S. BRAUER, JOHN C. PEARSON, BRIAN J. DROUIN, SHANSHAN YU, JET PROPULSION LABORATORY, CALIFORNIA INSTITUTE OF TECHNOLOGY, 4800 OAK GROVE DR., PASADENA, CA TC 06 (2009) THE SUBMILLIMETER SPECTRUM OF CH 3 CH 2 CN IN ITS GROUND VIBRATIONAL STATE. CAROLYN S. BRAUER, JOHN C. PEARSON, BRIAN J. DROUIN, SHANSHAN YU, JET PROPULSION LABORATORY, CALIFORNIA INSTITUTE OF TECHNOLOGY, 4800 OAK GROVE DR., PASADENA, CA

3 Background 6/19/2014RA 04 Literature Daly, A. M., Bermúdez, C., & López, A, B. Tercero 2, J. C. Pearson 3, N. Marcelino 4, J. L. Alonso 1, and J. Cernicharo , ApJ, 768, 81 Fukuyama Y, Omori K, Odashima H, Takagi K, Tsunekawa S: Analysis of rotational transitions in excited vibrational states of propionitrile (C2H5CN). Journal of Molecular Spectroscopy 1999, 193(1): Mehringer DM, Pearson JC, Keene J, Phillips TG: Detection of vibrationally excited ethyl cyanide in the interstellar medium. Astrophysical Journal 2004, 608(1): Brauer CS, Pearson JC, Drouin BJ, Yu SS: NEW GROUND-STATE MEASUREMENTS OF ETHYL CYANIDE. Astrophysical Journal Supplement Series 2009, 184(1): Duncan, N.E., Janz, G.J. Molecular Structure and Vibrational Spectroscopy of Ethyl Cyanide, Journal of Chemical Physics Mader H, Heise HM, Dreizler H: MICROWAVE-SPECTRUM OF ETHYL CYANIDE - R0-STRUCTURE, NITROGEN QUADRUPOLE COUPLING-CONSTANTS AND ROTATION-TORSION-VIBRATION INTERACTION. Z Naturfors Sect A-J Phys Sci 1974, A 29(1): Laurie VW: MICROWAVE SPECTRUM AND INTERNAL ROTATION OF ETHYL CYANIDE. Journal of Chemical Physics 1959, 31(6): Lerner RG, Dailey BP: MICROWAVE SPECTRUM AND STRUCTURE OF PROPIONITRILE. Journal of Chemical Physics 1957, 26(3):

4 HOT CORE COMPONENT 1 (4’’, 5 Km s -1 respect to LSR, 5 Kms -1 line width ) HOT CORE COMPONENT 3 (25’’, 3 Km s -1 respect to LSR, 22 Kms -1 line width ) Parameters of the Orion-KL region that best simulate the emission line profile of CH 3 CH 2 CN using the “Excitation and transfer code” (J. Cernicharo, 2012) Temperature and column density derived from analysis of rotational transitions of CH 3 CH 2 CN define the physical and chemical conditions of the Orion-KL region. N (cm -2 )275 K130 K65 K N(CH 3 CH 2 CN g.s.) (cm −2 ) (3.0±0.9)x10 16 (8±2)x10 15 (3.0±0.9)x10 15 N(CH 3 CH 2 CN ν 13 =1/ ν 21 =1) N(CH 3 CH 2 CN ν 20 ) (cm −2 ) N(CH 3 CH 2 CN ν 12 ) (cm −2 ) (4 ±1)x10 15 (1.7 ±0.5)x10 15 (6 ±3)x10 14 (1.1±0.3)x10 15 (4±1)x10 14 (1.6±0.5)x10 14 (4±1)x10 14 (1.7±0.5)x10 14 (6±3)x10 13 N( 13 CH 3 CH 2 CN) (cm −2 ) N(CH 3 13 CH 2 CN) (cm −2 ) N(CH 3 CH 2 13 CN) (cm −2 ) (7 ±2)x10 14 (2±1)x10 14 (1.9±0.6)x10 14 (5±3)x10 13 (7±2)x10 13 (1.7±0.8)x10 13 Ethyl cyanide ORION-KL Nebula CH 3 CH 2 CN LABORATORY MEASUREMENTS – RADIO ASTRONOMICAL OBSERVATIONS LABORATORY MEASUREMENTS – RADIO ASTRONOMICAL OBSERVATIONS A-CH 2 DCH 2 CN, S-CH 2 DCH 2 CN, CH 3 CHDCN) “upper limit for the N (cm -2 ) (tentative detection)” HOT CORE COMPONENT 2 (10’’, 3 Km s -1 respect to LSR, 13 Kms -1 line width )

5 Frequency range 6/19/2014RA 04 SourceFrequency Range Valladolid Stark GHz Valladolid FM GHz, Toyoma Line list GHz OSU Line FASST a GHz JPL , GHz JPL , GHz, THz a S. M. Fortman, I. R. Medvedev, C. F. Neese, and F. C. De Lucia. ApJ725, 1682 (2010).

6 Stark spectroscopy 6/19/2014RA 04 Daly, A. M., Bermúdez, C., & López, A, B. Tercero 2, J. C. Pearson 3, N. Marcelino 4, J. L. Alonso 1, and J. Cernicharo , ApJ, 768, 81

7

8 Background 6/19/2014RA 04 AuthorsStatesFrequency Range Bauer, et alG.S.Up to 1.6 THz Fukuyama Mehringer D.M. et al v 13, v 21 Up to 40 GHz Up to 300 GHz Fukuyama Daly, et al v 20 Up to 40 GHz Up to 600 GHz Daly, et alv 12 Up to 600 GHz Fortman, et al.All states GHz

9 6/19/2014RA 04 Calc Energy cm -1 A”A’A”A’ Coriolis(a,b)Fermi strongCoriolis(a,b) Coriolis(a,b)Darling-Dennison(e-e) weak v 13 Coriolis(a,b) Calc Energy cm -1 A’A”A’ CoriolisFermi v 13 Coriolis v 21 The Hamiltonians

10 6/19/2014RA 04 StateVibrational E E Lower Range J Ave Energy – G.S. Energy Predicted Energy** Predicted anharmonic energyPercent anharmonic GS v v * *two points removed ** MP2/aug-cc-pVTZ K=0&1 Data sets in the De Lucia Temperature Study

11 2v 13 K 0&1 v 20 K 0&1 2v 21 K 0&1 V 13 +V 21 K 1&2 2v 13 K 1&2 2v 21 K1&2 v 20 K 2&3 v 20 K 1&2 V 13 +V 21 K 0&1 2v 13 K 2&3 2v 21 K 2&3

12 K=0&1 and K=1&2 series 4 state fit 2v 21 K 0&1 v 20 K 2&3 v 20 K 1&2v 20 K 0&1 2v 13 K 0&1 2v 13 K 1&2 2v 21 K1&2 V 13 +V 20 K 0&1 V 13 +V 21 K 1&2

13 6/19/2014RA 04 2v 13 K 2&3 2v 21 K 2&3 V 13 +V 21 K 2&3? 2v 21 K1&2 2v 13 K 1&2 ? V 13 +V 21 K 1&2 V 13 +V 21 K 0&1

14 K=1&2 2V Series 4 &5 K=1&2 2V Series 4 &5 K=1&2 V13+V Stack T fat K=1&2 vt= K=1&2 GS K=1&2 Vbo K=1&2 Vbi= K=1&0 2V Already K=1&0 2V Assigned K=1&0 V K=1&2 2V series a from ppt these? series a from PPT these? K=1&0 GS V21+V13 K=1& Series P&Q Series P&Q K=1&0 Vop K=1&0 vbi= K=1&0 2V Already K=1&0 2V Assigned Color Scheme in Loomis-Wood Plot

15 6/19/2014RA 04 K=0&1 series 3 state fit v 20+ v 21 v 20+ v 13 v 12

16 Signal Strength 6/19/2014RA 04 v ,54 →57 5, ,59 →59 2,58 A/E v 20 +v ,59 →59 1,58 A/E G.S, 57 6,51 →56 6,50

17 6/19/2014RA K a = 0, 1 and 2 K a = 0K a = 1 K a = 2 0 from g.s same transition Lower Upper v 20 analysis

18 6/19/2014RA K a = 3, 4, 5 K a = 3 K a = 4 K a = 5 Lower Upper v 20 analysis

19 6/19/2014RA K a = 3 perturbation 20 K a =3 with 2 13 and 2 21 K a =0 & 1 Kc=odd interaction (a,b) symmetry Perturbations in v 20

20 6/19/2014RA K a = 4 perturbation Perturbations in v 20

21 6/19/2014RA K a = 4 perturbation Perturbations in v 20

22 6/19/2014RA K a = 6, 7, 8, 9 K a = 6 K a = 7 K a = 8 K a = 9 v 20 analysis

23 6/19/2014RA cm -1 Energy levels of v20

24 6/19/2014RA 04 Calc Energy cm -1 A”A’A”A’ Coriolis(a,b)Fermi strongCoriolis(a,b) Coriolis(a,b)Darling-Dennison(e-e) weak v 13 Coriolis(a,b) Calc Energy cm -1 A’A”A’ CoriolisFermi v 13 Coriolis v 21 Conclusion - Under construction

25 Future Studies Continue work on excited vibrational states – v 20, 2v 13, 2v 21, v 21 +v C isotopes from University of Lille – Assign G.S. up to 1.6 THz – Assign the v 21 /v 13, v 20, v 12 – 232, 223 and 322 – Freq: Ghz J= 9-13 a-dipole K=0 – GHz J= a-dipole K=0 – GHz J= a-dipole K=0 – GHz but 940 GHz is highest recognized transition of ground state ( R-branch J=52, Ka=11)JPL – JPL – GHz using chain of the 1.1 THz source and final tripler removed. – GHz using new chain – 1p0, 1p1, 1p4 and 1p5 was measured by SYu GHz 6/19/2014RA 04

26 Acknowledgements John C. Pearson Shanshan Yu Brian J. Drouin Celina Bermúdez José Luis Alonso Caltech Postdoctoral Scholarship Program Herschel project at JPL 6/19/2014RA 04