1. Analysis of the 18 O 3 CRDS spectra in the 6000 – 7000 cm -1 spectral range : comparison with 16 O 3. Marie-Renée De Backer-Barilly, Alain Barbe, Vladimir G. Tyuterev Groupe de Spectrométrie Moléculaire et Atmosphérique, UMR CNRS 6089, Université de Reims Champagne Ardenne, Moulin de la Housse, BP 1039 - 51687 REIMS Cedex 2, France Eugeniya Starikova Laboratory of Theoretical Spectroscopy of IAO SB RAN, av. Akademicheskii 1, 634055 TOMSK, Russia. Alain Campargue, Samir Kassi, Anwen Liu. Laboratoire de Spectrométrie Physique, UMR CNRS 5588, Université Joseph Fourier, BP 87 - 38402 Saint Martin d'Hères Cedex, France. During the last two years, we have investigated the high energy levels of the 16 O 3 molecule 1, and references herein, approaching the dissociation limit (~8000 cm -1 ) from high sensitivity CW-CRDS spectra recorded in Grenoble. The spectra of the totally substituted 18 O 3 isotopologue have been also recorded in the same 6000 – 7000 cm -1 spectral range in order to provide complementary information on the Potential Energy and the Dipole Moment Surfaces. Up today, 15 bands (10 A-type bands and 5 B-type bands) have been observed and analyzed in that range. We present here the results of the analyses : range of observed quantum numbers and rms for each observed band ; parameters of the effective Hamiltonian and effective transition moment, and several comparisons between observed and calculated spectra for selected spectral regions. The comparison between the vibrational energies predicted from the potential function and the observed band centers will be discussed for the the 18 O 3 isotopologue and the 16 O 3 molecule. Reference 1- A. Campargue, A. Barbe, M.-R. De Backer-Barilly, Vl. G. Tyuterev and S. Kassi Phys. Chem. Chem. Phys., 10, 2925-2946, (2008). Summary Photodiode Lambdameter Optical isolator Laser diode Coupler AO Modulator laser ON Laser OFF -50050 100 threshold =f(T,I) 6nm/diode 40 diodes The fibered CW- CRDS spectrometer Spectral region: 1480-1687 nm (5800-7000 cm -1 ) Routine sensitivity 3  10 -10 cm -1 Experimental setup 18 O 3 16 O 3 Sym.Exp. (cm -1 )(Obs.-Calc.) a P 1 (%) b W1W1 P 2 (%)W2W2 P 3 (%)W3W3 Exp. (cm -1 ) (Obs.-Calc.) a P 1 (%) b W1W1 P 2 (%)W2W2 P 3 (%)W3W3 B5984.439 - 0.4 48.7(025) 0 10.9(223) 0 9.1(313) 0 6305.047 - 0.846.3(025) 0 14.3(313) 0 12.2(115) 0 A6011.836 0.1 72.2(430) 0 9.8(322) 0 8.7(124) 0 6365.264 -1.348.3(430) 0 17.4(214) 0 8.8(322) 0 B6013.304 0.3 74.5(501) 0 21.9(303) 0 3.0(105) 0 6355.722 - 0.273.4(501) 0 22.6(303) 0 3.3(105)0 A6047.100 0.6 41.1(214) 0 17.2(124) 0 13.6(412) 0 B6072.132 1.5 27.8(115) 0 27.1(313) 0 22.5(223) 0 6386.997 - 0.928.0(223) 0 20.4(313)018.8(115)0 A6244.942 - 0.5 49.1(016) 0 22.8(304) 0 9.6(106) 0 A6267.367 0.2 61.6(350) 0 18.2(044) 0 13.4(242) 0 B6270.601 0.06 43.6(205) 0 28.1(403) 0 12.3(115) 0 6586.967 - 2.332.3(205) 0 20.9(421)020.0(403)0 B6392.213 -1.6 39.2(233_1) 0 22.9(143) 0 11.4(035) 0 6716.536 - 0.531.8(233_1) 0 23.7(143)010.2(125)0 B6556.787 - 2.5 37.8(035) 0 13.4(323) 0 12.1(125) 0 6895.493 0.220.5(035) 0 20.0(063)012.8(171)0 A6592.661 - 0.07 29.6(134) 0 25.0(224) 0 10.0(422) 0 B6611.038 1.0 68.4(511) 0 16.3(313) 0 5.9(007) 0 6981.870 0.665.1(511) 0 15.8(313)08.0(007)0 B6642.893 0.7 33.9(233_2) 0 12.3(323) 0 9.2(125) 0 6990.069 -2.332.1(233_2) 0 14.8(035)012.0(431)0 B6796.463 - 0.2 38.0(125) 0 16.0(431) 0 15.9(413) 0 B6825.551 - 0.2 38.2(431) 0 19.8(323) 0 10.6(233) 0 Notes: a Difference between the vibrational energy values obtained from the experimental data reduction with variational predictions calculated [1] from the PES of Ref. [2]. b Columns 4-9 represent three major contributions for the decomposition of corresponding wave functions derived from the potential function [2, 3] in normal mode coordinates q 1, q 2, q 3 using 10th order Contact Transformations [1]. Columns Pn’s indicate the mixing coefficients (in %) of  eff in the harmonic normal mode basis. Columns Wn’s indicate the corresponding vibration normal mode quantum numbers (v 1 v 2 v 3 ) 0. n is the order of the contribution. The subscript “0” of (v 1 v 2 v 3 ) 0 means the normal mode representation. Comparison of the observed band centers with the theoretical predictions C 18 O 2 C 16 O 2 Overview of the 18 O 3 CRDS spectra H2O 2 2 +5 3 5 1 + 3 1 + 2 +5 3 1 + 2 +5 3 2 1 +5 3 3 2 +5 3 2 1 +3 2 +3 3 Sym.Exp.(v 1 v 2 v 3 ) 0 a Transitions b J maxK a maxLevels rms (×10 3 cm -1 ) B5984.439(025) 0 5073512284 A6011.836(430) 0 3237722 B6013.304(501) 0 5663814312 9.52 A6047.100(214) 0 18438587 B6072.132(115) 0 5993512306 A6244.942(016) 0 9242250 A6267.367(350) 0 519,22,26137.3 B6270.601(205) 0 6593713330 B6392.213(233_1) 0 3503361919.3 B6556.787(035) 0 5743712344 18.0 A6592.661(134) 0 339486171 B6611.038(511) 0 254356163 B6642.893(233_2) 0 355349234 B6796.463(125) 0 3843092136.2 B6825.551(431) 0 1642771026.5 Total : 5064Total : 2812 Notes : a Dominant normal mode contribution in eigenvector expansion (see previous Table). b Number of transitions rovibrationally assigned Range of upper state quantum numbers for the transitions included in the fits Example of comparaison between Observed and Calculated Spectra References 1.Vl. G. Tyuterev, S. A. Tashkun and H. Seghir, to be published. 2.Vl. G. Tyuterev, S. A. Tashkun, P. Jensen, A. Barbe and T. Cours, J. Mol. Spectrosc., 1999, 198, 57–76. 3.Vl. G. Tyuterev, S. A. Tashkun, D. W. Schwenke, P. Jensen, T. Cours, A. Barbe and M. Jacon, Chem. Phys. Lett., 2000, 316, 271–279. Overview of the 2 1 +5 3 and 2 +6 3 bands : 6200 – 6300 cm -1 region Example of agreement in the R-branch of the 2 1 +5 3 band Observed spectrum Calculated spectrum Observed spectrum Calculated spectrum Example of assignments in the P-branch of the 2 1 +5 3 band (with some lines of the 2 +6 3 band: assignment in red) Calculated spectrum Observed spectrum P19 0 P14 7 12 C 16 O 2 P17 4 Q19 10 12 C 18 O 2 P15 6 P16 5 P18 2 P10 9 Q15 11 27 2 26  26 1 25 23 1 23  22 0 22 22 0 22  21 1 21 C 18 O P12 8 ; C 18 O Q22 9 Q16 9