1. Synchrotron-Based High Resolution Spectroscopy of N-Bearing PAHs Sébastien Gruet, Olivier Pirali, Manuel Goubet and P. Bréchignac ISMS 2014 16/06/2014

2. Hypothesis : A. Leger, J. L. Puget, A&A 1984, 137, L5. Typical vibrational modes of aromatic compounds: (in µm) at : 3.3, 6.2, 7.7, 8.6, 11.3, 20.8, 27 and 56. (in cm -1 ) at ≈: 3030, 1612, 1298, 1162, 884, 480, 370, and 178. N-Bearing PAHs Peeters et al, 2002, A&A,390, 1089 Rotationally resolved IR data of PAHs in the literature Relatively recent and still scarce One of the first publication: S. Albert et al. Faraday Discuss. 150, 71-99 (2011) TA11 – Roger Adams Lab 116 – 11 h 35 to 11 h 50 AM Quinoline/Isoquinoline: Z. Kisiel et al. J. Mol. Spectrosc. 217, 115 (2003). Quinoxaline/Quinazoline: D. McNaughton, J. Chem. Phys. 124, 154305 (2011) 2

3. 3 Experimental device Room temperature long pathlength cell (150m) Bruker IFS 125 Resolution: 0.00102cm -1 ≈ 30MHz Bruker IFS 125 Resolution: 0.00102cm -1 ≈ 30MHz

4. 4 Resolution: 0.5cm -1 41 37 45 41 28 27 38 28 41

5. 5 Resolution: 0.00102cm -1 Butterfly Mode Drumhead Mode C-H oop Mode 28 41 18

6. 6 Effective Hamiltonian for asymmetric top molecules : Study of the out of plane vibrational modes : Selection rules for c-type transitions : Butterfly mode at ≈ 170 cm -1 c a b c

7. 7

8. Molecules IsoquinolineQuinolineQuinoxalineQuinazoline[1,5]-naphthyridine Parametersν 41 ν 37 ν 45 ν 41 ν 28 ν 27 ν 38 ν 22 ν 18 Band Center cm -1 /MHz 479.485171(14)/ 14374603.79(41) 824.847928(20)/ 24728318.78(60) 168.42685(17)/ 5049295.00(45) 476.29985(12)/ 14279110.35(37) 177.012852(23)/ 5306711.82(71) 399.989736(7)/ 11991390.62(21) 484.246528(17)/ 14490568.27(45) 166.238827(12)/ 4983714.66(37) 817.836519(14)/ 24518122.03(41) A /MHz 3198.15593(57)3198.07100(99)3141.720(10)3145.60425(49)3159.7236(10)3163.66994(17)3229.17317(69)3168.8103(22)3166.2677(22) B /MHz 1237.90868(25)1237.80930(90)1271.9964(10)1271.4866(21)1311.5359(21)1310.8785(11)1276.0753(61)1311.9904(52)1311.7859(47) C /MHz 893.0982(36)892.8501(13)906.4591(11)906.0809(31)928.0085(32)927.4615(16)915.3788(85)929.0061(52)928.3064(40) Δ J /kHz 0.01874(57)0.01826(39)0.0191578(70)0.019020(78)0.018624(53)0.01738(11)0.01516(19)0.019731(56)0.022130(60) Δ K /kHz 0.15373(33)0.16758(44)0.08477(12)0.16045(32)0.15570.1557(89)0.14871(67)0.17964(62)0.15799(49) Δ JK /kHz 0.04818(26)0.04760(19)0.056525(78)0.04765(28)0.03077(38)0.06348(58)0.07129(70)0.04967(37)0.04563(28) δ J /kHz 0.005454* 0.00596593(62)0.005662*0.005621* 0.005752*0.005862 δ K /kHz 0.061465* 0.0593144(76)0.060622*0.063420* 0.063307*0.061291 N of lines 277523572578266324722550209224691959 IR RMS 0.00016 cm -1 0.00024 cm -1 0.00020 cm -1 0.00017 cm -1 0.00019 cm -1 0.0018 cm -1 0.00021 cm -1 0.00015 cm -1 0.00019 cm -1 J” min /J” max 14/9917/8715/9415/9912/9915/8317/999/9911/91 Ka” min /Ka” max 14/6417/4314/5014/6012/4814/4117/529/51 8 9 rovibrational bands analyzed for these 5 molecules. Analysis of 3 other bands in progress. Determination of the GS constants of the [1,5]-napthyridine.

9. 9 Anharmonic DFT calculation at the B97-1/cc-pVTZ//ANO-DZP level Accurate calculated rotational parameters More details about calculations: M. Goubet, O. Pirali, J. Chem Phys. 140, 044322 (2014) Useful tool to begin the GSCD analysis by LWW diagram Quinoxaline ModeGS 27 ParametersCalculatedExperimentalDeviationCalculatedExperimentalDeviation A /MHz3166.078173165.90879-0.169373163.799743163.66994-0.12980 B /MHz1307.454861310.636923.182061307.664721310.878523.21379 C /MHz925.72913927.130481.40135925.93898927.461461.52247 Corrected Calculated Values ExperimentalDeviation 3163.630373163.669940.03957 1310.846781310.878520.03174 927.34034927.461460.12112 the B97-1/cc-pVTZ//ANO-DZP level Anharmonic DFT calculation at the B97-1/cc-pVTZ//ANO-DZP level

10. MoleculesQuinazolineQuinoline[1,5]-naphthyridine ModesGSν 38 GSν 45 ν 41 GSν 22 ν 18 Experimental-0.13619 -0.13406-0.12940 MoleculesQuinazolineQuinoline[1,5]-naphthyridine ModesGSν 38 GSν 45 ν 41 GSν 22 ν 18 Experimental-0.13619 -0.44721-0.13406-0.64132-0.36925-0.12940-0.68598-0.46407 MoleculesQuinazolineQuinoline[1,5]-naphthyridine ModesGSν 38 GSν 45 ν 41 GSν 22 ν 18 Calculated -0.12239-0.41006-0.12504-0.70649-0.37344-0.12718-0.67650-0.43612 Experimental-0.13619 -0.44721-0.13406-0.64132-0.36925-0.12940-0.68598-0.46407 MoleculesQuinazolineQuinoline[1,5]-naphthyridine ModesGSν 38 GSν 45 ν 41 GSν 22 ν 18 Calculated -0.12239-0.41006-0.12504-0.70649-0.37344-0.12718-0.67650-0.43612 Experimental-0.13619 -0.44721-0.13406-0.64132-0.36925-0.12940-0.68598-0.46407 Deviation-0.0138-0.0620-0.00900.06510.0041-0.0022-0.0094-0.0279 10 Check the reliability of our fitted rotational constants Contribution of the out of plane low frequency modes (GS) Correlation with the amplitude of the deformation motions (ES)

11. 11

12. Pure rotational transitions in the ES.  Collaboration: LPCA Dunkerque (Fr) & PhLAM Laboratory (Fr) & IP PAS (Pl) 12 Important database of rotational information in the IR  Simulation at different resolution and at low temperature Study of larger molecules : Jet-AILES Experiment (IPR, LADIR, PhLAM, SOLEIL) FA09 – Roger Adams Lab 116 – 11 h 01 to 11 h 16 AM