Laser induced dispersed fluorescence spectra of jet cooled NO2: The complete set of vibrational levels up to 10 000 cm−1 and the onset of the X̃ 2A1–Ã 2B2 vibronic interaction

The laser induced dispersed fluorescence spectra (L.I.D.F.S.) of jet cooled NO2 molecules in emission from 11 different vibronic levels located between 22 006 and 23 625 cm−1 was recorded. The corresponding variety of Franck–Condon accesses has allowed the observation of the complete set of the 191 lowest vibrational levels of the X 2A1 ground state, located up to 10 000 cm−1. The vibrational band origins were measured to within typically 0.3 cm−1, assigned (n1, n2, n3), and fitted with a 24 coefficient Dunham expansion giving a typical residual error of 0.5 cm−1. Furthermore, the vibrationless A 2B2 level has probably also been observed at 9737 cm−1. A perturbative model of the X 2A1–A 2B2 vibronic interaction has been used in order to calculate the energy shift of the high vibrational levels (around 10 000 cm−1) of the X 2A1 state.

[1]  R. Buenker,et al.  Abinitio MRD-CI study of NO2. 1. Multi-dimensional potential surfaces for the two lowest 2A′ states , 1985 .

[2]  W. J. Lafferty,et al.  High-resolution infrared spectrum of the ?2 + ?3 band of 14N16O2 , 1975 .

[3]  H. D. Bist,et al.  High vibrational levels and vibronic coupling in nitrogen dioxide , 1976 .

[4]  A. Douglas,et al.  THE ABSORPTION SPECTRUM OF NO2 IN THE 3 700-4 600 A REGION, , 1965 .

[5]  H. Foth,et al.  Analysis of the perturbed NO2 system in the 591.4- to 592.9-nm region based on sub-Doppler laser spectroscopy , 1983 .

[6]  P. A. Mello,et al.  Random matrix physics: Spectrum and strength fluctuations , 1981 .

[7]  E. Davidson,et al.  An ab initio potential‐energy surface study of several electronic states of NO2 , 1976 .

[8]  J. Brand,et al.  Anharmonic potential constants and the large amplitude bending vibration in nitrogen dioxide , 1976 .

[9]  J. Brand,et al.  The 2B1 ← 2A1 system of nitrogen dioxide☆ , 1973 .

[10]  W. J. Lafferty,et al.  High Resolution Infrared Spectra of the ν2 and 2ν1 Bands of 14N16O2 , 1975 .

[11]  J. Hardwick.  Fluorescence from the 2B1 state of NO2 excited at 4545 Å , 1977 .

[12]  R. Smalley,et al.  The fluorescence excitation spectrum of rotationally cooled NO2 , 1975 .

[13]  A. Delon,et al.  dispersed fluorescence spectra of glyoxal cooled in a supersonic jet: Energy and assignment of 264 S0 vibrational levels , 1988 .

[14]  K. Yamanouchi,et al.  Vibrational level structure of highly excited SO2 in the electronic ground state. II. Vibrational assignment by dispersed fluorescence and stimulated emission pumping spectroscopy , 1990 .

[15]  L. Cederbaum,et al.  Statistical fluctuations of decay rates , 1989 .

[16]  Zimmermann,et al.  Confirmation of random-matrix fluctuations in molecular spectra. , 1988, Physical review letters.

[17]  Ahsan Khan,et al.  The electronic structure of NO2. II. The ? 2B2← ? 2A1 and ? 2B1←? 2A1 absorption systems , 1976 .

[18]  C. Hause,et al.  Molecular constants for the (3, 0, 1) band of NO2☆ , 1970 .

[19]  Ernest R. Davidson,et al.  The two lowest energy 2A′ states of NO2 , 1976 .

[20]  H. C. Longuet-Higgins,et al.  Intersection of potential energy surfaces in polyatomic molecules , 1963 .

[21]  L. Cederbaum,et al.  The visible absorption spectrum of NO2: A three-mode nuclear dynamics investigation , 1985 .

[22]  C. Pei,et al.  An analytic formula of one-dimensional Franck-Condon factors for linear harmonic oscillators , 1990 .

[23]  J. Brown,et al.  Microwave spectroscopy of nonlinear free radicals - I. General theory and application to the Zeeman effect in HCO , 1973, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[24]  C. Hause,et al.  Upper state molecular constants for the (0, 0, 3) and (1, 0, 3) vibration-rotation bands of nitrogen dioxide , 1970 .

[25]  W. J. Lafferty,et al.  The high resolution infrared spectrum of the 2ν2 + ν3 and ν1 + ν2 + ν3 bands of 14N16O2 , 1977 .

[26]  W. Demtröder,et al.  Vibronic Level Density of Excited NO2‐States and its Statistical Analysis , 1988 .

[27]  M. Lombardi,et al.  NO2 jet cooled visible excitation spectrum: Vibronic chaos induced by the X̃ 2A1–Ã 2B2 interaction , 1991 .

[28]  R. P. Hosteny,et al.  The electronic structure of nitrogen dioxide. I. Multiconfiguration self‐consistent‐field calculation of the low‐lying electronic states , 1975 .