Rotational and Hyperfine Analyses of the Band of 17 O- Containing Isotopologues of Oxygen Measured by CRDS at Room and Liquid Nitrogen Temperatures Olga Leshchishina, Samir Kassi, Iouli E. Gordon, Shanshan Yu, Alain Campargue a 1  g — X 3  g -

Involved electronic states of oxygen a 1  g X 3 Σ g - M1- Magnetic dipole E2- Electric quadrupole M1, E2 Remote sensing in relation to high-accuracy measurements of atmospheric greenhouse gases such as CO 2 and CH 4 –Uniform mixing of oxygen provides calibration and removes systematic errors –ASCENDS mission Nightglow in planetary atmospheres M1>> E µm

Selection rules e f e f f e e e f e J=±2J=±2  J=±1  J=0 T(9)S(10) R(9)S(8) P(9)O(10) S(9)S(9) O(9)O(9) N(9)O(8)S(9)R(10) R(9)R(9)P(9)P(9) O(9)P(8) R(9)Q(10) Q(9)Q(9) P(9)Q(8) J N=9 F1F1 F2F2 F3F3 Q(9)R(8) Q(9)P(10) Notation of branches: ΔN(N'')ΔJ(J'')

CRDS measurements in Grenoble laser ON Laser diode Photodiode Lambdameter Optical isolatorCoupler AO Modulator Laser OFF threshold =f(T,I) 6nm/diode 9 DFB diodes Routine sensitivity: cm -1, ie 1 % absorbance for 300 km path length Large dynamic range of the measured intensities: absorption coefficients from to cm -1 are measured on a single spectrum

Unresolved hyperfine structure

The cryogenic cell

Resolving Hyperfine Structure

Relation of hyperfine splitting and observed transitions 16 O 17 O and 17 O 18 O

18 O 2

Summary of the observed transitions

Previous hyperfine work Cazzoli et al., Nuovo Cimeto B Serie 1981; 62: O 17 O and 17 O 18 O transitions between fine structure components within many rotational levels in the ground state. Cazzoli G, Degli Esposti C, Landsberg BM. Millimetre wave spectrum of 17 O 2. Magnetic hyperfine structure and quadrupole coupling constants. Nuovo Cimento D Serie 1984;3: Arrington Jr. CA, Falick AM, Myers RJ. Electron Paramagnetic Resonance Spectrum of O 2 (a 1  g ) - Its 17 O Hyperfine Coupling and Electronic and Rotational g Values. J Chem Phys 1971;55:

Details of the fit X 3  g X 3  g a1ga1ga1ga1g -

Results of the fit

Hyperfine constants 16 O 17 O 17 O 18 O 17 O 2 a (This work) (195) (261) (126) a (EPR)-424(1)

Conclusions Transitions of three 17 O-containing isotopologues of oxygen were measured in 1.27 µm region at room and liquid nitrogen temperatures. The experiments at 80 K allowed to significantly better resolve the hyperfine structure in the rotational lines even for 17 O 2. Rotational constants for the studies species in the ground state improved significantly. Most of the spectroscopic constants in the upper state and first vibrational level in the ground state were determined for the first time.

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