Grupo de Espectroscopa Molecular Lab de Espectroscopia y

Grupo de Espectroscopía Molecular, Lab. de Espectroscopia y Bioespectroscopia Edificio Quifima, Unidad Asociada CSIC, Universidad de Valladolid, Spain Departamento de Astrofísica, Centro de Astrobiología, CAB, CSIC-INTA, Madrid, Spain CNRS et Universités Paris Est et Paris Diderot, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), Creteil, France THE MILLIMETER-WAVE SPECTRUM OF VINYL ACETATE Lucie Kolesniková, Isabel Peña, José L. Alonso, José Cernicharo, Belén Tercero, Isabelle Kleiner International Symposium on Molecular Spectroscopy, June 16 20, 2014 Champaign-Urbana, Illinois, USA

Introduction and motivation § Methyl acetate (CH 3 COOCH 3) § Gauche-ethyl formate (g-CH 3 CH 2 OCOH) detected in ORION KLa detected in Sgr B 2 b a Tercero B. , Kleiner I. , Cernicharo J. , Nguyen H. V. L. , Lopez A. , and Muñoz Caro G. M. , 2013, Ap. J. 770, L 13. b Belloche, A. , Garrod, R. T. , Műller, H. S. P. , et al. 2009, A&A, 499, 215.

Introduction and motivation § Methyl acetate (CH 3 COOCH 3) § Gauche-ethyl formate (g-CH 3 CH 2 OCOH) detected in ORION KLa detected in Sgr B 2 b acetate containing molecules are potential candidates § Vinyl acetate (CH 3 COOCHCH 2) – one of the simplest unsaturated carboxylic ester § Previous data up to 77 GHzc → new data → search in Orion KL a Tercero B. , Kleiner I. , Cernicharo J. , Nguyen H. V. L. , Lopez A. , and Muñoz Caro G. M. , 2013, Ap. J. 770, L 13. b Belloche, A. , Garrod, R. T. , Műller, H. S. P. , et al. 2009, c Velino B. , Maris A. , Melandri S. , Caminati W. A&A, 499, 215. J Mol. Spectrosc. 256 (2009) 228 – 231.

Vinyl acetate molecule § Predicted conformersb DE = 0 cm 1 DE = 1060 cm 1 DE = 2313 cm 1 b Velino B. , Maris A. , Melandri S. , Caminati W. J Mol. Spectrosc. 256 (2009) 228 – 231.

Vinyl acetate molecule § The most stable conformer MP 2/6 -311++g(d, p): ma = 0. 04 D mb = 1. 62 D mc = 0. 09 D Velino et. al. b: V 3 = 155. 111 (93) cm 1 A-E splitting § Previous data (61 – 77 GHz)b predictions (BELGI-Cs) b Velino B. , Maris A. , Melandri S. , Caminati W. J Mol. Spectrosc. 256 (2009) 228 – 231.

CP-FTMW spectra: experiment § CP-FTMW spectrometer (6 – 18 GHz)c Supersonic Expansion 2 nozzels Ne carrier gas (2 bar) Broadband FT-MW spectrometer c S. Mata I. Peña, C. Cabezas, J. C. López and J. L. Alonso. J. Mol. Spectrosc. 280 (2012) 91– 96

CP-FTMW spectra: analysis 6 – 18 GHz

CP-FTMW spectra: analysis 6 – 18 GHz 211 202 110 101 A E 3 3 12 03 A E 111 000 E A 212 101 E A

CP-FTMW spectra: analysis 6 – 18 GHz 211 202 110 101 A E 3 3 12 03 A E 111 000 E A 212 101 E A

CP-FTMW spectra: analysis 6 – 18 GHz 211 202 212 101 111 000 110 101 A E E A E 3 3 12 03 E A A A E Parent species 13 C 4 18 O 1 18 O 2 2 A-lines: 1 1 0 1 13 C 3 13 C 1

CP-FTMW spectra: analysis 6 – 18 GHz 211 202 212 101 111 000 110 101 A E E A E 3 3 12 03 E A A A E assignments of the transitions of the parent species and isotopologues Parent species 13 C A-lines: 1 1 0 1 13 C 2 search for the second 3 conformer 1 4 18 O 1 18 O 2

CP-FTMW spectra: results A-species rotational constants (MHz) Parent species 13 C 13 C 2 3 13 C 4 18 O 1 2 A 9436. 2220 (86) 9424. 5281 (92) 9421. 2015 (98) 9435. 194 (12) 9296. 1454 (58) 9344. 686 (11) 8895. 465 (23) B 2243. 1532 (16) 2178. 0120 (46) 2223. 9524 (21) 2234. 434 (17) 2202. 5830 (27) 2241. 8028 (91) 2220. 264 (24) C 1832. 4004 (17) 1788. 2639 (27) 1819. 0190 (29) 1826. 6583 (69) 1800. 0171 (16) 1828. 0230 (48) 1796. 027 (12) Substitution coordinates (Å) Atom (assumption of the symmetry plane) |a| |b| C 1 2. 60635 (58) 0. 2641 (57) C 2 1. 3989 (11) 0. 2953 (51) C 3 0. 9314 (17) 0. 080 (19) C 4 2. 04148 (74) 0. 9132 (16) O 1 0. 2625 (57) 0. 5179 (29) O 2 1. 0793 (14) 1. 2982 (12)

MMW spectra: experiment § MMW and sub-MMW spectrometer (50 – 1000 GHz) 129 – 360 GHz room temperature 20 mbar

MMW spectra: experiment § MMW and sub-MMW spectrometer (50 – 1000 GHz) 129 – 360 GHz room temperature 20 mbar Synthesizer Sample cells Lock-in amplifier AM chains Lens

MMW spectra: experiment § MMW and sub-MMW spectrometer (50 – 1000 GHz) Detector Synthesizer Sample cells Lock-in amplifier AM chains Lens Roof-top mirror

MMW spectra: analysis MMW spectrum E A E A EA A

MMW spectra: analysis ncent (MHz) AABS package: http: //info. ifpan. edu. pl/~kisiel/aabs. htm Dn (MHz)

MMW spectra: analysis ncent (MHz) Ka’’ = 3, 4 E A Ka’’ = 2, 3 E A Ka’’ = 1, 2 E A Ka’’ = 0, 1 E A Dn (MHz)

MMW spectra: analysis ncent (MHz) Ka’’ = 3, 4 E A Ka’’ = 2, 3 E Ka’’ = 1, 2 A E A Ka’’ = 0, 1 E A CP-FTMW + MMW spectra > 1400 transitions (A-species) J’’ = 95, Ka’’ = 16 > 900 transitions (E-species) J’’ = 95, Ka’’ = 10 BELGI-Cs code (rho-axis method) Dn (MHz)

CP-FTMW + MMW spectra: results Operatora Current fit: J’’ = 75 18 floated torsion-rotation parameters F constant fixed to the value obtained by XIAM (Velino B. , Maris A. , Melandri S. , Caminati W. J Mol. Spectrosc. 256 (2009) 228 – 231. ) Constant Unit Value Pa 2 A cm-1 0. 3026567 (31) Pb 2 B cm-1 0. 0848837 (11) Pc 2 C cm-1 0. 061139775 (45) {Pa, Pb} Dab cm-1 -0. 047932 (45) {Pa, Pc}(sin 3 ) Dac cm-1 0. 000639 (13) -P 4 DJ x 10 -8 cm-1 0. 52753 (48) -Pa 4 DK x 10 -6 cm-1 0. 31561 (46) -2 P 2(Pb 2 -Pc 2) J x 10 -9 cm-1 0. 8538 (24) -2 Pa 2(Pb 2 -Pc 2) K x 10 -8 cm-1 0. 957 (17) P 2 F cm-1 [5. 56622] (1/2)(1 -cos 3 ) V 3 cm-1 158. 5748 (44) Pa. P unitless P 2 (Pa Pb + Pb Pa) Dab x 10 -5 cm-1 0. 638 (35) (1 -cos 3 )Pa 2 k 5 x 10 -2 cm-1 0. 32990 (94) (1 -cos 3 )P 2 FV x 10 -3 cm-1 -0. 147 (75) (1 -cos 3 )(Pb 2 -Pc 2) c 2 x 10 -4 cm-1 -0. 7546 (79) (1 -cos 3 ){Pa, Pb} d. AB cm-1 -0. 0000973 (60) Pg. Pa P 2 Lv cm-1 -0. 0000001372 (44) P 4 Pa 2 HJK x 10 -13 cm-1 0. 270 (40) a In the rho-axis system 0. 0457062 (35)

CP-FTMW + MMW spectra: results Operatora Constant Unit Value Pa 2 A cm-1 0. 3026567 (31) Pb 2 B cm-1 0. 0848837 (11) cm-1 0. 061139775 (45) P C New laboratory data up to 360 GHz 2 c {Pa, Pb} D cm -0. 047932 (45) principal axis-system -1 ab {Pa, Pc}(sin 3 ) Dac cm-1 0. 000639 (13) -P 4 DJ x 10 -8 cm-1 0. 52753 (48) -Pa 4 DK x 10 -6 cm-1 0. 31561 (46) x 10 -2 P (P -P ) New set of the spectroscopic constants x 10 -9 cm-1 0. 8538 (24) -8 cm-1 0. 957 (17) 2 b 2 2 c J -2 Pa 2(Pb 2 -Pc 2) Current fit: K P 2 F cm-1 [5. 56622] (1/2)(1 -cos 3 ) V 3 cm-1 158. 5748 (44) Pa. P unitless Dab x 10 P 2 (Pa Pb + Pb Pa) J’’ = 75 Search for the vinyl acetate in Orion KL (1 -cos 3 )Pa 2 k 5 x 10 -2 18 floated torsion-rotation FV x 10 -3 (1 -cos 3 )P 2 parameters 2 2 -4 -5 F constant fixed to the value obtained by XIAM (Velino B. , Maris A. , Melandri S. , Caminati W. J Mol. Spectrosc. 256 (2009) 228 – 231. ) 0. 0457062 (35) cm-1 0. 638 (35) cm-1 0. 32990 (94) cm-1 -0. 147 (75) (1 -cos 3 )(Pb -Pc ) c 2 x 10 cm-1 -0. 7546 (79) (1 -cos 3 ){Pa, Pb} d. AB cm-1 -0. 0000973 (60) Pg. Pa P 2 Lv cm-1 -0. 0000001372 (44) P 4 Pa 2 HJK x 10 -13 cm-1 0. 270 (40) a In the rho-axis system

Acknowledgements Grants CTQ 2010 - 19008, AYA 2009 -07304 and AYA 2012 -32032 CSD 2009 -00038 Molecular Astrophysics …and all the members of the Grant VA 070 A 08