Determination of NO (v=0–7) product distribution from the N(4S)+O2 reaction using two‐photon ionization

The product vibrational state distribution for the reaction N(4S)+O2→NO(2Π,v)+O has been measured using saturated multiphoton ionization spectroscopy to determine NO electronic ground‐state distributions. The fraction of the reaction exothermicity appearing in product vibration is 〈 f v〉=0.34; however, the even vibrational levels (v=0,2,4,6) are relatively overpopulated with respect to the odd vibrational levels (v=1,3,5). It is not possible to obtain a good linear‐surprisal fit to all the data, but the even and odd subsets fit quite well to individual surprisal plots. The results are compared with previous measurements, including a reanalysis of laser‐excited fluorescence data corrected for electronic transition moment and Franck–Condon factor variations. Collisional relaxation is observed at high O2 pressures for NO levels v=4 through 7, and is fit with a phenomenological relaxation model.

[1]  J. Steinfeld,et al.  Evaluation of 2-photon ionization spectroscope as a probe of NO ground state population distributions , 1986 .

[2]  M. Bowers,et al.  Product energy disposal in the reaction of N+(3P) with O2(X 3Σ) , 1986 .

[3]  H. Zacharias,et al.  Rotational and electronic relaxation in pulsed supersonic beams of NO seeded in He and Ar , 1984 .

[4]  M. E. Whitson,et al.  Nitric oxide vibrational excitation from the N(4S)+O2 reaction , 1983 .

[5]  B. D. Green,et al.  The vibrational relaxation of NO(v = 1–7) by O2 , 1982 .

[6]  J. Gibson,et al.  Rate constants for formation of NO in vibrational levels v = 2 through 7 from the reaction N(4S)+O2→NO‡+O , 1981 .

[7]  J. Milewski,et al.  Shock‐tube CO2 gas‐dynamic laser operating on the (0310)⇄(10°0) transition at 18.4 μm , 1981 .

[8]  P. Benioff,et al.  A study of the minimum energy path of the reaction N(4S) + O2(3Σ−g) → NO(2Πu) + O(3P) , 1980 .

[9]  H. Zacharias,et al.  State selective step-wise photoionization of NO with mass spectroscopic ion detection , 1980 .

[10]  B. Bederson,et al.  Atom—Molecule Collision Theory: A Guide for the Experimentalist , 1980 .

[11]  D. Albritton,et al.  Production of NO+(a 3Σ+) ions in the reaction of N+ ions with O2 at 300 K , 1979 .

[12]  W. A. Payne,et al.  Absolute rate of the reaction of N(4S) with NO from 196–400 K with DF–RF and FP–RF techniques , 1978 .

[13]  B. Green,et al.  Nitric oxide chemiexcitation occurring in the reaction between metastable nitrogen atoms and oxygen molecules , 1978 .

[14]  A. C. Wahl,et al.  Ab initio calculations of the minimum energy path in the doublet surface for the reaction N(4S)+O2(3Σ−g) →NO(2Πu) +O(3P) , 1977 .

[15]  M. E. Whitson,et al.  Vibrational energy distribution in the NO produced by the reaction of N(4S) with O2 , 1976 .

[16]  A. A. Likal’ter Laser utilizing transitions between levels of paired CO2 modes , 1975 .

[17]  C. Wilson Diatomics‐in‐molecules potentials for N(4S) collisions with O2(3Σg−) , 1975 .

[18]  A. Barbe,et al.  Infrared spectra of 16O3 and 18O3: Darling and Dennison resonance and anharmonic potential function of ozone , 1974 .

[19]  F. Kaufman,et al.  Reactions of Metastable Nitrogen Atoms , 1971 .

[20]  P. E. Rouse,et al.  The β and γ bands of nitric oxide observed during the flash photolysis of nitrosyl chloride , 1971 .

[21]  R. Wayne,et al.  Kinetics of the reaction between atomic nitrogen and molecular oxygen in the ground (3∑-g) and first excited (1∆g) states , 1970, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[22]  R. G. Rehm,et al.  Vibrational Relaxation of Anharmonic Oscillators with Exchange‐Dominated Collisions , 1968 .

[23]  R. C. Sahni,et al.  Quantum mechanical treatment of molecules. Part 4.—RKR Franck-Condon factors for the γ and β band systems of the NO molecule , 1968 .

[24]  R. W. Nicholls Franck-Condon Factors to High Vibrational Quantum Numbers IV: NO Band Systems. , 1964, Journal of research of the National Bureau of Standards. Section A, Physics and chemistry.

[25]  R. J. Spindler,et al.  Franck-Condon factors for the β and γ bands of the NO molecule based on realistic potential functions , 1964 .

[26]  B. Thrush,et al.  Kinetics of the reactions of active nitrogen with oxygen and with nitric oxide , 1961, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[27]  David M. Dennison,et al.  The Water Vapor Molecule , 1940 .