1. Update of the analysis of the pure rotational spectrum of excited vibrational states of CH 3 CH 2 CN Adam Daly, John Pearson, Shanshan Yu, Brian Drouin Jet Propulsion Laboratory Celina Bermúdez, José Luis Alonso Universidad de Valladolid, Grupo de Espectroscopia Molecular 6/23/2015TG- 061

2. Astronomy Research Demands As Pepe Cernicharo stated to me “analyze, assign and publish everything for every molecule”. http://www.herschel.caltech.edu/image/nhsc2010-003a 6/23/2015TG- 062

3. C 2 H 5 CN Ethyl Cyanide 6/23/2015TG- 06 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 2 2013, ApJ, 768, 81 v12, v20 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):72- 103. V13-v21-v20. Mehringer DM, Pearson JC, Keene J, Phillips TG: Detection of vibrationally excited ethyl cyanide in the interstellar medium. Astrophysical Journal 2004, 608(1):306-313. V13-v21 Brauer CS, Pearson JC, Drouin BJ, Yu SS: NEW GROUND-STATE MEASUREMENTS OF ETHYL CYANIDE. Astrophysical Journal Supplement Series 2009, 184(1):133-137 gs Duncan, N.E., Janz, G.J. Molecular Structure and Vibrational Spectroscopy of Ethyl Cyanide, Journal of Chemical Physics 1955 23 434-440. gs 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):164-183. Gs, v13-v21 Laurie VW: MICROWAVE SPECTRUM AND INTERNAL ROTATION OF ETHYL CYANIDE. Journal of Chemical Physics 1959, 31(6):1500-1505 Lerner RG, Dailey BP: MICROWAVE SPECTRUM AND STRUCTURE OF PROPIONITRILE. Journal of Chemical Physics 1957, 26(3):678- 680. 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 ) 6/23/2015TG- 064

5. Frequency range 6/23/2015TG- 06 SourceFrequency Range Valladolid Stark18-110 GHz Valladolid FM50-170 GHz, 270-360 Toyoma Line list26-200 GHz OSU Line FASST a 258-368 GHz JPL270-318, 395-605GHz JPL200-260, 680-800 GHz, 940- 1.5 THz a S. M. Fortman, I. R. Medvedev, C. F. Neese, and F. C. De Lucia. ApJ725, 1682 (2010). 5

6. 6/23/2015TG- 06 StateVibrational E E Lower 570-640 Range J 67-75 Ave Energy – G.S. Energy Predicted Energy** Predicted anharmonic energyPercent anharmonic GS0725 ---- 13 200895169203 0.0 21 2009612362232163.1 20 36911153903753711.1 2 13 40011684434074060.2 2 21 40011834584464254.7 21 +v 13 4001152427426.94211.3 12 53012735485345300.7 20 +v 13 57412985735785750.5 20 + 21 * 57412134885985812.8 *two points removed ** MP2/aug-cc-pVTZ K=0&1 Data sets in the De Lucia Temperature Study 6

7. 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 6/23/2015TG- 067 Assignments of low K a series for  13, 2 21, 13 + 21 Calc Energy cm -1 A”A’A”A’ 374 20 Coriolis(a,b)Fermi strongCoriolis(a,b) 406 2 13 Coriolis(a,b)Fermi (e-e) weak 421 21 +v 13 Coriolis(a,b) 425 2 21

8. 6/23/2015TG- 06 K a =0&1 series 3 state fit v 20+ v 21 v 20+ v 13 v 12 8 Calc Energy cm -1 A’A”A’ 530 12 CoriolisFermi 575 20 +v 13 Coriolis 581 20 +v 21

9. Signal Strength 6/23/2015TG- 06 v 12 58 5,54 →57 5,53 60 2,59 →59 2,58 A/E v 20 +v 13 60 1,59 →59 1,58 A/E G.S, 57 6,51 →56 6,50 9

10. 6/23/2015TG- 06 20 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 10

11. 6/23/2015TG- 0611 General Philosophy Construct a Hamiltonian to fit the Fukuyama, et al. dataset Is there splitting in 20 because of the perturbation?

12. 6/23/2015TG- 0612 The 20 splitting in the b-dipole can it be fit? Do we need an interaction Coriolis or Fermi with 2 13,2 21 or 13 + 21 ?

13. 6/23/2015TG- 0613 Building the interaction Hamiltonian in SPFIT for 20 (A″) Coriolis or Fermi interaction 1.Attempt an isolated state fit 2.Build in approximate interaction terms

14. 6/23/2015TG- 0614 263: 11 3 9 1 10 3 8 1 98687.3020 0.1333 0.050 264: 12 3 10 1 11 3 9 1 107677.8840 -0.0132 0.050 265: 13 3 11 1 12 3 10 1 116669.9180 0.0558 0.050 266: 14 3 12 1 13 3 11 1 125661.8080 -0.0281 0.050 267: 15 3 13 1 14 3 12 1 134652.5360 0.1287 0.050 268: 16 3 14 1 15 3 13 1 143640.0370 0.0279 0.050 269/ 6 3 3 2 5 3 2 2 53783.4450 0.2254 0.050 270: 7 3 4 2 6 3 3 2 62762.3280 0.0222 0.050 271/ 8 3 5 2 7 3 4 2 71749.0380 -0.1993 0.050 272: 9 3 6 2 8 3 5 2 80745.7970 -0.1262 0.050 273: 10 3 7 2 9 3 6 2 89754.4020 -0.1230 0.050 274: 11 3 8 2 10 3 7 2 98777.4060 -0.0781 0.050 275: 12 3 9 2 11 3 8 2 107817.5170 -0.0184 0.050 276: 13 3 10 2 12 3 9 2 116877.6960 0.0102 0.050 277: 14 3 11 2 13 3 10 2 125961.1600 0.0072 0.050 278: 15 3 12 2 14 3 11 2 135071.2900 0.0388 0.050 279: 16 3 13 2 15 3 12 2 144211.3240 0.1080 0.050 280/ 5 4 2 1 4 4 1 1 44804.7920 0.3924 0.050 281/ 6 4 3 1 5 4 2 1 53770.0650 0.1919 0.050 282: 7 4 4 1 6 4 3 1 62737.9490 0.0991 0.050 283: 8 4 5 1 7 4 4 1 71708.8440 0.1004 0.050 284/ 10 4 7 1 9 4 6 1 89661.0020 0.1713 0.050 285/ 11 4 8 1 10 4 7 1 98642.0330 -0.5696 0.050 286/ 12 4 9 1 11 4 8 1 107629.1800 0.7155 0.050 287/ 13 4 10 1 12 4 9 1 116618.4410 -0.3075 0.050 288/ 14 4 11 1 13 4 10 1 125613.5310 -0.1988 0.050 289: 15 4 12 1 14 4 11 1 134613.3960 -0.1104 0.050 MICROWAVE lines fitted lines lines RMS RMS ERROR J range Ka range total dv=0 dv.ne.0 UNFITTD e>900 v"= 0 183 183 0 5 0 0.198298 3.96597 2 16 0 4 v"= 1 83 68 15 1 0 0.199442 3.98884 3 16 0 4 v"= 2 95 87 8 5 0 0.137774 2.75549 2 16 0 4 -------------------------------------------------------------------------------------------- total: 361 338 23 11 0 0.184592 3.69183 This fit has opened the door to the THz analysis of the b-dipole transitions

15. 6/23/2015TG- 0615 StateEnergy A state v 13 -5.06 MHz v 21 45.25 MHz v 20 -18.38 MHz Summary of A-E energy difference

16. 6/23/2015TG- 0616 Using this current model, we have assigned over 800 transitions and plan to analyze the perturbations at K=3,4 and at high K of 20 with the other states 13 CH 3 CH 2 CN, CH 3 13 CH 2 CN and CH 3 CH 2 13 CN A- state has been assigned for 21 /  13,  12 and 20 and currently fitting 21 /  13 up 1 THz 13 C isotopes from University of Lille. More updates: These fits will be published soon!

17. 6/23/2015TG- 0617 Acknowledgements Caltech- JPL John Pearson Brian Drouin Tim Crawford GEM-Valladolid José Luis Alonso Jose Cernicharo Celina Bermúdez Alicia López Professor Kisiel