First high resolution analysis of the 53 band of nitrogen dioxide (NO2) near 1.3 µm

Didier Mondelain1, Agnès Perrin2, Samir Kassi1 &

Alain Campargue1

1 Laboratoire Interdisciplinaire de Physique Univ. Grenoble 1 / CNRS, LIPhy UMR 5588, Grenoble, F-38041, France

2 Laboratoire Inter-Universitaire des Systèmes Atmosphériques (LISA), UMR 7583 CNRS et Univ Paris-Est Créteil & Paris

Diderot, 94010 Créteil, France

NO2: some importants points• Rotational constants: • A~8.0023 , B~0.4337 and C~0.4104 cm-1

• .1~1320 cm-1 2~750 cm-1; 3~1617 cm-1

• C-type Coriolis resonance is coupling the (v1,v2,v3)(v1,v2+2,v3-1) energy levels

• C-type Coriolis resonance is coupling the (1,0,0)(0,0,1) energy levels

• These exists a « electron-spin – rotation » interaction which splits each energy level in two spin-rotation components (considered for all vibrational states)

• Hyperfine structure (I(N)=1): had to be considered for the (0,0,0) and (0,1,0) vibrational states.

NO2 : already existing studies (v1,v2,v3)

• (0,0,0)• (0,1,0)• (1,0,0)(0,2,0)(0,0,1)• (0,3,0)(0,1,1)• (1,1,0)• (1,2,0)(1,0,1)• (0,4,0)(0,2,1)(0,0,2)• (2,2,0)(2,0,1)• (0,2,2) (0,0,3)• (1,2,2) (0,8,0) (1,0,3)• (4,2,0) (4,0,1) (0,9,0)

• 0• 750• 1616.• 2355• 2063• 2906.• 3092.• 4180• 4754• 5984• 6677 cm-1

)1v,2v,v(v,v,v 321321

)0,0,1(1,0,0

C-type Coriolis

Last two studies

1+33 band (5984.7 cm-1) S. Miljanic et al. Journal of Molecular Spectroscopy 251 (2008) 9–15 (FTS spectra recorded at Créteil, in France)

.41+3 band: 6676.9 cm-1: Perrin et al. , JQSRT 111 (2010) 2246–2255 CW-Cavity Ring Down Spectroscopy (Grenoble in France)

NO2 : already existing studies (v1,v2,v3)

• (0,0,0)• (0,1,0)• (1,0,0)(0,2,0)(0,0,1)• (0,3,0)(0,1,1)• (1,1,0)• (1,2,0)(1,0,1)• (0,4,0)(0,2,1)(0,0,2)• (2,2,0)(2,0,1)• (0,2,2) (0,0,3)• (1,2,2) (0,8,0) (1,0,3)• (4,2,0) (4,0,1) (0,9,0)

• 0• 750• 1616.• 2355• 2063• 2906.• 3092.• 4180• 4754• 5984• 6677 cm-1

Higher order resonances

C-type Coriolis

)0,0,1(1,0,0

)1v,2v,v(v,v,v 321321

How can we get informations on the dark states of NO2 ??????

Delon & Jost. “Laser induced dispersed fluorescence spectra of jet cooled NO2: The complete set of vibrational levels up to 10 000 cm-1 & the onset of the X2A1-~2B2

vibronic interaction”, J. Chem. Phys. 95 (8), 15 October 1991

Delon & Jost. J. Chem. Phys. 95 (8), 15 October 1991

)1v,2v,v(v,v,v 321321 C-type Coriolis resonances

Delon & Jost. J. Chem. Phys. 95 (8), 15 October 1991

C-type Coriolis resonancesHigher order resonances

The 41+3 band of NO2.Perrin, Kassi & Campargue, JQSRT 111, 2246, (2011)

Higher order resonances

(4,2,0)(4,0,1) C-type Coriolis resonances

Outlook• The first high-resolution absorption spectrum of the 53

band (0,0,5)-(0,0,0) vibrational transition) of 14N16O2 in the 7766.070 cm-1 region

• High sensitivity CW-Cavity Ring Down Spectroscopy between 7674 and 7795 cm-1. (Grenoble’s group)

• The set of the (0,0,5) spin-rotation energy levels were reproduced within their experimental uncertainty using a theoretical model which takes explicitly into account the Coriolis interactions between the spin rotational levels of the (0,0,5) vibrational state and those of the (0,2,4) dark state

• The electron spin-rotation resonances within the (0,0,5) and (0,2,4) states were also accounted for.

• NO higher order Coriolis resonances

Experimental detailsThe high-sensitivity absorption spectrum of nitrogen dioxide was

recorded at 1.3 µm by CW-Cavity Ring Down spectroscopy (fibered distributed feedback (DFB) spectrometer [2-5]) in Grenoble.

Each of the 16 different DFB laser diode has a typical tuning range of about 35 cm-1 by temperature tuning from -10°C to 60°C.

Stainless steel CRDS cell (l= 1.4 m, inner diameter F= 10 mm) fitted by a pair of super-mirrors whose reflectivity allows for ring down times ranging

from 74 to 166 ms. About 20 to 30 ringdown events were averaged for each spectral data point, and the complete temperature scan of one DFB

laser last for about 65 minutes.Noise equivalent absorption min ~ 1×10-10 cm-1.

Pressure P= 5.0 or 10.0 Torr; Temperature T= 294.3K. [2] Macko, Romanini, Mikhailenko, Naumenko, Kassi, Jenouvrier , et al. J

Mol Spectrosc 2004;227:90.[3] Morville, Romanini, Appl. Phys 2004;D78:465.

[4] Perevalov, Kassi, Romanini, Perevalov, Tashkun, Campargue. J Mol Spectrosc 2006;238:241.

[5] Barbe, De Backer-Barilly, Tyuterev, Kassi, and Campargue J Mol Spectrosc 2011 , in press

Impurities: water and HF

Overview of the 1.6 µm region

)1v,2v,v(v,v,v 321321 C-type Coriolis resonances

Hamiltonian matrix

3 band

1007 lines N 47, Ka 9

Statistical analysis of the results  

Number of spin-rotation levels: 531

0 ≤ ≤ 0.002 cm–1 66.7 %

0.002 ≤ ≤ 0.004 cm–1 25.8 %

0.004 ≤ ≤ 0.008 cm–1 7.5 %

Standard deviation: 0.1310–2 cm–1

1calcobs cminEE

Results of the analysis and of the Energy levels calculations

WExp

(0,0,1) – (0,2,0) 0.01041109 [PERR92]

(0,1,1) – (0,3,0)0.010519(11)

[PERR94]

(0,2,1) – (0,4,0)0.0108851(79)

[PERR96]

(0,0,2) – (0,2,1)0.0099108(25)

[PERR96]

(1,0,1) – (1,2,0)0.010651(29)

[MAND97]

(2,0,1) – (2,2,0)0.01004(11)

[STEP00]

(0,0,3) – (0,2,2)0.010600(53)

[STEP00]

(1,0,3) – (1,2,2)0.0108687(76)

[MILJ08]

(4,0,1)-(4,2,0)0.012500(53)

[PERR10]Average: 0.010159(7)

(0,0,5)-(0,2,4) 0.00688(32)This work

322C1

1v2,v,vv,v,v v1v2v2Wh321321

C-type Coriolis resonances

)1v,2v,v(v,v,v 321321

1hCiNy

1hCiNy +2hC {iNy,Nz2}+…

Conclusion

• The first analysis of the 53 band of NO2 was performed using high resolution cavity ring-down laser spectra recorded at 1.3 µm

• The Hamiltonian matrix accounts for the (0,0,5)(0,2,4) C-type Coriolis resonance and for the spin-rotation within (0,0,5) and (0,2,4).

• No higher order C-type Coriolis was observed, contrary to what was observed for the (4,0,1) and (1,0,3) vibrational states.