1. 11 The THz spectrum of GlycolAldehyde M. Goubet, T.R. Huet, I. Haykal, L. Margulès PhLAM, CNRS – Université de Lille 1 O. Pirali, P. Roy AILES beamline, synchrotron SOLEIL OSU ISMS – June 20-24 2011 Laboratoire de Physique des Lasers, Atomes et Molécules Tél. +33 (0)320 434785 | Fax. +33 (0) 320 337020 www-phlam.univ-lille1.fr

2. 2 stable isomers of the chemical formula C 2 H 4 O 2 GlycolAldehyde (GA) detected in the ISM prebiotic molecule (simpliest sugar) Acetic Acid (AA) detected in the ISM various industrial apps (most abundant carboxylic acid): polymers, drugs, food ads, solvents MethylFormate (MF) detected in the ISM few industrial apps (harmful and flammable): insecticide, drugs, refrigerant The THz spectrum of GlycolAldehyde OSU ISMS – June 20-24 2011

3. 3 Astrophysical interest Regions of characteristic signals of COMs Support to space observation missions (Herschel, Alma, …) Inaccurate extrapolations from mm-waves Spectroscopic interest Large amplitude motions and intermolecular modes are in the FIR Low excitation energy = non-destructive probing  access to the dynamic, conformational and structural properties. Why from the mm-waves to FIR regions ? MF - 18 O spectrum @ 100 K The THz spectrum of GlycolAldehyde OSU ISMS – June 20-24 2011

4. 4 The GA spectrum: background No FIR spectrum of GA (dimeric powder in standard conditions) C-C torsion ( 1 ) ~ 200 cm -1 (very weak) C-C-O bend ( 2 ) ~ 300 cm -1 (weak) C-OH torsion ( 3 ) ~ 370 cm -1 (medium) + hot and combination bands M. L. Senent, J. Phys. Chem. A 108 (2004) 6286 Previous studies in the cm-, mm- and submm-waves regions: M. Rey et al., Chem. Phys. Lett. 430 (2006) 121. K.-M. Marstokk et al., J. Mol. Struct. 5 (1970) 205. R.A.H. Butler et al., ApJS 134 (2001) 319. S.L. Widicus-Weaver et al., ApJS 158 (2005) 188. P.B. Carroll et al., ApJ 723 (2010) 845.  global fit including all data The THz spectrum of GlycolAldehyde OSU ISMS – June 20-24 2011

5. 55 The GA spectrum: new data in the THz region The r Q branch (J~55, Ka=36) P = 0.030 mbar, T = 294 K, 780 – 950 GHz region. The Lille spectrometer See talks: FA07 – FA08 – FA09 The THz spectrum of GlycolAldehyde OSU ISMS – June 20-24 2011

6. 66 Data in the 2-1300 GHz range from Lille/Oslo/Columbus/JPL fitted at the experimental accuracy: ParameterThis WorkCaroll et alParameterThis WorkCaroll et al A18446.26463(24)18446.25696(134)  J x 10 9 -7.200(16)-7.710(170) B6525.998019(86)6525.99578(51)  JK x 10 9 172.47(18)170.86(168) C4969.235650(91)4969.23452(50)  KJ x 10 9 -811.39(46)-825.6(57)  J x 10 3 6.221459(58)6.21986(47)  K x 10 9 1076.37(77)1060.9(65)  JK x 10 3 -20.38811(33)-20.39838(219)  J x 10 9 -2.1338(21)-2.2752(253)  K x 10 3 47.71178(68)47.6959(36)  JK x 10 9 -26.139(91)-25.42(105)  J x 10 3 1.834568(12)1.833997(112)  K x 10 9 286.3(12)309.6(174)  K x 10 3 8.86289(31)8.8676(45)L J x 10 12 0.335(13)0.0776(222) J max 8063L JJK x 10 12 -0.358(26)0.211(203) K max 3732L JK x 10 12 -4.009(74)-3.90(65) N of Lines38481412L KKJ x 10 12 22.07(18)26.65(154) Fit rms0.0430.061L K x 10 12 -28.52(31)-21.82(252) Ground state parameters (in MHz) The THz spectrum of GlycolAldehyde OSU ISMS – June 20-24 2011

7. 77 Data in the 2-950 GHz range from Lille/Oslo/Columbus/JPL fitted at the experimental accuracy: Excited states results 1 2 3 This workpreviousThis workpreviousThis workprevious J max 776176487639 K max 351435153215 N of Lines 222167220654911882340 Fit RMS (MHz) 0.0520.1300.0530.1290.0540.120 The THz spectrum of GlycolAldehyde OSU ISMS – June 20-24 2011

8. 88 The GA spectrum: new data in the FIR (Soleil SR + IFS125HR + long pass cell) @ Ailes beamline: High brightness in the FIR: less scans needed White type multipass cell: absorption length = 150 m  High sensitivity for low vapor pressure samples. The THz spectrum of GlycolAldehyde OSU ISMS – June 20-24 2011

9. 99 The GA spectrum: new data in the FIR The THz spectrum of GlycolAldehyde OSU ISMS – June 20-24 2011 3 (1←0) 3 (2←1) 2 (1←0) 1 (1←0) 1 (2←1) 1 (3←2) 1-3 (?←?) HR (10 -3 cm -1 ) spectrum of GA (< 10 -2 mb) @ AILES – long pass (150 m) cell

10. 10 The GA spectrum: new data in the FIR Wavenumber / cm -1 The THz spectrum of GlycolAldehyde OSU ISMS – June 20-24 2011

11. 11 1 (1 ← 0) 2 (1 ← 0) 3 (1 ← 0) Band origin207.6 (199.3) 282.4 (294.0) 360.3 (368.7) Jmax50 80 Kmax112338 No of Lines38237195868 Fit RMS0.000300.000150.00033 Accuracy0.000470.0002350.00047 Global fit: vibrational results (in cm -1 ) Data in the 150-450 cm -1 range fitted at the experimental accuracy: In parenthesis: ab initio values from M. L. Senent, JPCA 108 (2004) 6286 The THz spectrum of GlycolAldehyde OSU ISMS – June 20-24 2011

12. 12 The GA spectrum: perspectives Analysis of the hot and combination bands x 3-3, x 1-1 and x 1-3 anharmonicity constants Intramolecular H-bond properties (C-OH torsion not perturbed and high ~ 350 cm -1 / e.g. Ethanol ~ 200 cm -1 ) The THz spectrum of GlycolAldehyde OSU ISMS – June 20-24 2011 Experimental and a- and b- type sticks spectrum of 2 3 (2←1)

13. 13 Acknowledgments Financial funding: ANR « TopModel » (ANR-08-BLAN-0054) ; Programme PCMI and many thanks for your attention T. Huet P. RoyO. Pirali L. Margulès I. Haykal 13 Laboratoire de Physique des Lasers, Atomes et Molécules Tél. +33 (0)320 434785 | Fax. +33 (0) 320 337020 www-phlam.univ-lille1.fr