Electronic States and Band Spectrum Structure in Diatomic Molecules. IV. Hund's Theory; Second Positive Nitrogen and Swan Bands; Alternating Intensities

Robert S. Mulliken
Phys. Rev. 29, 637 – Published 1 May 1927
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Abstract

After a brief review of Hund's theory of molecular electronic states and band spectra, and a discussion of intensity relations and selection principles in terms of the correspondence principle, it is shown that practically all the available evidence, as embodied in previous papers of this series and elsewhere, is in agreement with the theory. The occurrence of ρ-type S terms and σ-type P and D terms is explained by the theory, as also the existence of ρ-type and σ-type doubling. Selection rules and other relations in P2S2 and S2P2 transitions (including, in agreement with Mecke and Hulthén, the CH, OH, MgH, and CaH bands) are discussed. Hund's interpretation of the second positive nitrogen bands as a P3P3 transition is further developed, and extended to the Swan bands; the apparent absence of Q branches, and other intensity relations in these bands, are explained; the rotational doubling in these bands (accompanied by alternating intensities) is interpreted as σ-type doubling. It is shown that the alternating intensities or alternate missing lines in the He2, N2, Swan, and N2+ bands can all be accounted for formally by the postulate that they are due to alternate (partially or completely) suppressed levels such that the suppressed values of (jkσk) are always as follows: B rotational sub-states, (j12σk)=0, 2, 4, ; A sub-states, 1, 3, 5,...; here σk is the part of σ which is due to the orbital angular momentum of the electron, and jk is the resultant of σk and the quantity m which measures the nuclear angular momentum in quantum units.—Finally, the questions of term-notation and -formulation, j values for odd and even molecules, etc., are considered. The NH β bands (P3S3) are briefly discussed.

  • Received 12 February 1927

DOI:https://doi.org/10.1103/PhysRev.29.637

©1927 American Physical Society

Authors & Affiliations

Robert S. Mulliken

  • Washington Square College, New York University

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Issue

Vol. 29, Iss. 5 — May 1927

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