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The Beta Bands of Nitric Oxide. I. Measurements and Quantum Analysis

Francis A. Jenkins*, Henry A. Barton*, and Robert S. Mulliken

  • Jefferson Physical Laboratory, Harvard University, Washington Square College, New York University

  • *National Research Fellow.

Phys. Rev. 30, 150 – Published 1 August, 1927

DOI: https://doi.org/10.1103/PhysRev.30.150

Abstract

Band structure and wave-number data for band lines. Using an active nitrogen source, the β bands of NO included in the region of 2300 to 5300A have been photographed in the second order of a 21-ft. Rowland concave grating. Each complete band consists of two sub-bands with a P and an R branch of the ordinary type and also a very weak Q branch. The latter is relatively more intense in the lower frequency sub-band. Here there are four missing lines in the otherwise continuous PR series, while there are two in the higher frequency sub-band. The lines of the latter are narrow doublets superficially resembling those of the violet CN bands. The six branches for each of eighteen bands have been measured, and wave-numbers are tabulated for 20 to 30 lines in the P and R branches, and for the few visible members of the Q branches. The bands measured include nine of the strong n=0 progression (n=4 to 12), three of n=1(n=6, 11, 13), four of n=2(n=9, 13, 14, 15), and two of n=3(n=8, 16).

Isolation and representation of spectral terms. Combinations involving the P and R branches are found to hold, and show the existence of four different sets of rotational terms, two (one for each sub-band) in the initial electronic state and similarly two in the final state. For low values of j the rotational terms in all four cases are representable by F(j)=B(j2σ2). From a consideration of the missing lines, the observed transitions are classified as P12P12. with σ=σ=12, for the higher frequency system, and P22P22, σ=σ=32, for the lower frequency system. A table is given of the weighted mean values of Δ2F in the observed vibrational states of the initial and final electronic levels, and another of the empirical coefficients in analytical expressions for Δ2F(j) and F(j). Certain anomalies in the form of the latter in particular the appreciable difference in B for the components of a doublet, are shown to be a necessary consequence of Hund's theory of molecular electronic states as applied quantitatively to doublet states by E. C. Kemble. These effects are found to be larger in the initial state, thus showing, according to the theory, that the doublet separation must be smaller here than in the final state. Equations for the band origins are obtained (Eqs. 8 of the text) which permit a representation of the vibrational energy levels; in these, cubic and biquadratic terms are both definitely required, and when they are included the observed values are reproduced with a mean error of 0.03 cm1.

Constants of the nitric oxide molecule. The moment of inertia I0 and the internuclear distance r0 for the vibrationless molecules are evaluated as I0=(24.80±0.02)×1040 gr cm2, I0=(16.30±0.02)×1040, r0=1.418×108 cm, r0=1.150×108. B, the coefficient of j2 in F(j), is represented within experimental error by the linear relation B=B0αn, where for the P12 bands B0=1.0704, B0=1.6754, α=0.01162, α=0.01783, and for the P22 bands B0=1.1678, B0=1.7239, α=0.01892, α=0.01866. The β bands exhibit a longer series of n values than any system yet investigated in respect to the variation of B with n. Equations are given which permit a quantitative representation of the frequencies of all observed lines (Eqs. (2), (8), and (6) in conjunction with Table IV). From the equations for band-origins, the following quantities are obtained for the vibration frequency ω0 for infinitesimal amplitudes, P12 bands, ω0=1029.43 cm1, ω0=1892.12, xω0=7.460, xω0=14.424; P22 bands ω0=1030.88, ω0=1891.98, xω0=7.455, xω0=14.454. The change of ω0 (and also of r0 and I0) during the emission is exceptionally great. Since the final state of the NO β bands is the normal state of nitric oxide, the above values of I0, r0, ω0, etc., apply to this state. An integration of the vibration frequency curve for the final state to the point of dissociation is carried out to determine the heat of dissociation.

Electronic states and relation to other bands. The doublet separation (for the rotationless molecule) in the initial P2 state is 32.9 cm1, if that in the final P2 state is taken as 124.4 in accordance with Frl. Guillery's data on the γ("third positive nitrogen") bands of NO. Only the difference between these (91.54 cm1) can be accurately found from the β bands. (See Fig. 1). The γ bands have the final doublet level in common with the β bands; hence all constants derived for the final state of the β bands apply equally well to that of the γ bands. The ultra-violet O2+ bands and certain SiN bands, whose structure is like that of the NOβ bands, are probably also P2P2 transitions.

See Also

The Beta Bands of Nitric Oxide. II. Intensity Relations and Their Interpretation

Henry A. Barton, Francis A. Jenkins, and Robert S. Mulliken
Phys. Rev. 30, 175 (1927)

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