1. The Millimeter- and Submillimeter-Wave Spectrum of Propenal A. M. DALY, C. BERMÚDEZ, L. KOLESNIKOVÁ, AND J. L. ALONSO Grupo de Espectroscopia Molecular Laboratorios de Espectroscopia y Bioespectroscopia Edificio Quifima. Parque Científico Universidad de Valladolid SPAIN ISMS 2014

2. Propenal Acrolein trans cis 0 cm -1 600 cm -1 Simplest conjugated adlehyde Sugar descomposition Amino acid formation MethionineGlutamic acid ISMS 2014

3. Is propenal in the ISM? Propanal [4] 6 lines 2 lines Propinal [4] 1 line Sagitarius B2 Green Bank 18-26 GHz ISMS 2014 Propenal [4] [1] Sagdeev R.Z. et al. Nature 1986; [2] Matthews H.E. et al. ApJ 1985; [3]Hollis J.M.et al. ApJ 2000; [4]Hollis J.M. et al. ApJ 2004 Glycoaldehyde [3] Acetaldehyde [2] Formaldehyde [1]

4. Detection of propenal Propenal 2 lines 2 1 1 – 1 1 0 3 1 3 – 2 1 2 Sagitarius B2 Green Bank 18-26 GHz 26079.449(1) MHz 18221.164(2) MHz ISMS 2014 No more lines belonging to propenal have been detected in the ISM [4]Hollis J.M. et al. ApJ 2004

5. 1955 [5] 1957 [6] 1966 [7] 1975 [8] 1982 [9] 1984 [10] ISMS 2014 Previous spectroscopy data trans cis 0 cm -1 600 cm -1 μ a = 3.06(4)D [6] μ b = 0.54(14)D μ a = 2.010(5)D [9] μ b = 1.573(3)D Rotational spectroscopy 36 GHz, t gs, t ν 18 36 GHz, t gs, t ν 18, t 2ν 18, t 3ν 18 27 GHz, t gs, t 1-9ν 18, isotopologes 13 C, 18 O, D 50 GHz, c gs, c ν 18 180 GHz, t gs Year 50 GHz, c gs, c ν 18 isotopologes 13 C, 18 O, D GHz measured [5] Fine et al. JChemPhys. 1955; [6] Wagner R. et al. JChemPhys 1957; [7] Cherniak E.A. et al. JChemPhys 1966; [8] Winniwisser M. et al. Z. Naturforsch. 1975; [9] Bolm et al. ChemPhysL 1982; [10] Blom et al. JACS 1984

6. Previous spectroscopy data trans cis 0 cm -1 600 cm -1 μ a = 3.06(4)D [6] μ b = 0.54(14)D μ a = 2.010(5)D [9] μ b = 1.573(3)D ISMS 2014 High resolution Far-IR Spectroscopy [11] t ν 18 t ν 13 t ν 13 + t ν 18 t 3ν 18 t ν 12 t ν 17 t 4ν 18 t ν 13 + t 2ν 18 t 2ν 13 t gs t 2ν 18 [11] McKellar A.R.W. et al. JMolSpectrosc. 2008.

7. Our goals ISMS 2014 Improving propenal rotational parameters Facilitate the detection of more transitions belonging to propenal ALMA project

8. Our goals ISMS 2014 Improving propenal rotational parameters trans cis 0 cm -1 600 cm -1 Analyze the rotational spectrum of higher energy vibrational excited states Extent the measurements of the vibrational excited states t gs and t ν 18 Measurements at higher frequency range of the t gs isotopologues at natural abundance Analyze the rotational parameters of c gs at higher frequency ranges

9. Vibrational excited state energies ISMS 2014 Interactions C-type Coriolis and Fermi trans

10. Stark spectrometer frequency range has been extended up to ~110 GHz Stark modulation spectroscopy ISMS 2014

11. Stark modulation spectroscopy Trans-propenal t ν 18 t ν 13 t ν 18 + t ν 13 t 3ν 18 t ν 12 t ν 17 t ν 13 + t 2ν 18 t 2ν 13 t gs t 2ν 18 t 4ν 18 4 1 4 – 3 1 3 t ν 13 t ν 12 t ν 17 t 2ν 13

12. MMW and sub-MMW spectrum MMW and sub-MMW spectrometer (50 – 1000 GHz) AM chains Synthesizer 50-110 GHz, 135 – 480 GHz, 500 – 700 GHz room temperature 15 mTorr Lock-in amplifier Sample cells Detector ISMS 2014 RJ05 Lucie Kolesniková Medical Science Building 2:28pm

13. t 3ν 18 ISMS 2014 MMW and sub-MMW spectrum t ν 13 t 2ν 18 t ν 13 + t ν 18 t gs t ν 18 Δν (MHz)

14. ISMS 2014 MMW and sub-MMW spectrum t ν 18 t gs t 2ν 18 t ν 13 t ν 13 + t ν 18 t 3ν 18

15. Interactions ISMS 2014 G c /MHz-365.03(44 ) G c J /MHz0.00273(45 ) G c K /MHz-0.2957(74 ) F ab /MHz-4.676(73 ) W/MHz82914.88(73 ) W +- /MHz0.09921(46 ) W +- J /MHz-4.77(188) ·10 -6 W +- K /MHz2.345(69) ·10 -3 W J /MHz-0.3067(208) W JK /MHz-2.655(50 ) ·10 -3 W KK /MHz0.5124(97 ) W/MHz134543.7(102) W +- /MHz0.2125(59 ) W +- J /MHz-0.143(46 ) ·10 -6 W J /MHz-0.5387(59 ) W JK /MHz-2.964(177) ·10 -3 W KK /MHz-41.45(138) F ab /MHz2.5449(50 ) G c /MHz556.928(90 ) G c /MHz-0.00099(83 ) G b /MHz-0.00657(42 ) G b /MHz0.03454(65 ) G b K /MHz-0.000135(204)

16. E/MHz[157.1704856][314.221907][323.0193961][468.94762][482.826622] A/MHz47353.68940(245)45782.7002(100)44391.655(141)48738.976(140)43110.34(97)46941.35(89) B/MHz4659.499457(87)4666.24203(33)4673.03078(136)4659.19801(138)4679.7384(80)4665.1109(78) C/MHz4242.689474(78)4259.627077(290)4276.62788(181)4238.34635(179)4293.4019(96)4255.9631(93) Δ J /kHz1.0420990(300)1.086567(95)1.132468(159)1.027465(157)1.19007(40)1.06501(34) Δ JK /kHz -8.78184(86)-8.53124(133)-8.2104(98)-10.3003(91)-7.681(42)-10.284(42) Δ K /kHz 358.149(149)-79.96(40)-331.2(49)828.1(78)-255.9(162)74.8(95) δ J /kHz0.1202562(102)0.118495(62)0.116641(136)0.118088(134)0.116358(203)0.112165(260) δ K /kHz5.7747(36)-0.6888(275)-6.237(62)11.559(65)-6.536(131)3.053(84) Φ J /mHz0.3142(39)0.5668(141)0.3803(120)0.4040(124)0.5938(161)0.3101(191) Φ JK /mHz8.62(164)128.9(59)-251(149)-39.1(171)-88.7(178)835.5(178) Φ KJ /mHz-507.4(62)460.5(193)2293(64)-1107(67)3002(109)-2120(107) Φ K /Hz-75.5(35)-555.8(60)[-75.5]348.1(153)4194(227)5030(261) φ J /mHz0.07667(159)0.1066(78)-0.017(225)0.0653(249)0.2119(225)0.193(32) φ JK /mHz8.78(85)44.7(49)[8.78] φ K /Hz1.977(222)16.56(79)-33.77(207)-2.45(248)4.37(272)133.9(315) L JJK / μ Hz 0.0532(244)-0.468(35) L JK / μ Hz -46.40(173)-162.81(160) L K /mHz828(32)2707.8(264) Fitting ISMS 2014 t ν 18 t gs t 2ν 18 t ν 13 t ν 13 + t ν 18 t 3ν 18 NσNσ 8571,213 98kHz

17. Alone6 states fitRef [8]Ref [11] A/MHz 47353.7105(14)45782.7002(100) 47353.7106(44) 45783.0348(87) B/MHz 4659.499489(51)4666.24203(33) 4659.49924(19) 4666.24289(96) C/MHz 4242.689471(46)4259.627077(290) 4242.68964(19) 4259.6272(10) Δ J /kHz 1.042053(16)1.086567(95) 1.04153(33) 1.086028(93) Δ JK /kHz -8.78484(6)-8.53124(133) -8.78252(28) -8.5460(50) Δ K /kHz 360.421(38)-79.96(40) 359.91(46) -65.72(21) δ J /kHz 0.1202785(66)0.118495(62) 0.119849(84) 0.11831(67) δ K /kHz 5.7400(22)-0.6888(275) 5.7986(22) -0.851(21) Φ J /mHz 0.2960(21)0.5668(141)... Φ JK /mHz -6.489(39)128.9(59) -12.3(53) Φ KJ /mHz -509.6(10)460.5(193) -475.6(93) Φ K /Hz...-555.8(60) φ J /mHz 0.07535(96)0.1066(78) φ JK /mHz 3.43(54)44.7(49) φ K /Hz 16.56(79) L JJK / μ Hz -0.468(35) L JK / μ Hz -162.81(160) L K /mHz 2707.8(264) Ground state trans ISMS 2014 [8] Winniwisser M. et al. Z. Naturforsch. 1975; [11] McKellar A.R.W. et al. JMolSpectrosc. 2008

18. 13 C isotopologues ISMS 2014

19. Cis isomer ISMS 2014

20. Rotational parameters ISMS 2014 t gsTrans 13 C 1 Trans 13 C 2 Trans 13 C 3 c gs A/MHz 47353.7105(14) a 47254.920(93)46518.557(92)46781.158(97)22831.6481(43) B/MHz 4659.499489(51) 4520.79373(27) 4642.43806(33) 4644.74078(37) 6241.04754(35) C/MHz 4242.689471(46) 4126.64224(32) 4221.74680(32) 4225.83687(37) 4902.20752(21) Δ J /kHz 1.042053(16) 0.988653(90) 1.03242(13) 1.03950(14) 5.11348(24) Δ JK /kHz -8.78484(38) -8.9420(15) -8.7379(15) -8.6746(34) -29.1849(12) Δ K /kHz 360.421(53) 366.31(52) 320.7(10) 312.46(36) 108.03(12) δ J /kHz 0.1202785(66) 0.111299(30) 0.121082(25) 0.120490(39) 1.48125(12) δ K /kHz 5.7400(22) 5.534(19) 5.556(13) 5.404(23) 11.3388(74) ΦJ/mHz 0.2960(21) 0.228(15) 0.399(22) 0.171(26) 1.649(89) ΦKJ/mHz -509.6(10) -399.7(80)-525.9(73) -413.(27)-1152.7(21) ΦJK/mHz -6.489(39)[0.] 92.30(47) φJ/mHz 0.07535(96)[0.] 1.111(43) φJK/mHz 3.43(54)[0.] -18.6(20) N lines c 1152,13401,10446,10419,10573,13 σ fit c /kHz 29,942,244,542,138,7 3 2 1

21. ISMS 2014 Summary The spectrum of propenal has been measured up to 700GHz Rotational parameters of the vibrational excited states below 600cm -1 has been obtained The analysis of c gs t gs and its isotopologues has been updated up to 700MHz Now it is time for you to find more lines of propenal in the interestllar medium

22. Acknowledgments Grants CTQ 2010- 19008 BES 2011-047685 CSD 2009-00038 Molecular Astrophysics Grants VA070A08 and CIP13/01 Grupo de Espectroscopia Molecular (GEM) Laboratorios de Espectroscopia y Bioespectroscopia, Unidad Asociada CSIC, UVa,Valladolid, Spain