On the Interpretation of the Rotational Structure of the CO2 Emission Bands

Robert S. Mulliken
Phys. Rev. 42, 364 – Published 1 November 1932
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Abstract

Schmid's analysis of the rotational structure of a number of the ultraviolet CO2 emission bands is discussed, and it is pointed out that in spite of uncertainties, some definite conclusions can be drawn, notably that the molecule in equilibrium is nearly linear, or probably strictly linear, in both initial and final states, that B is nearly equal to B, and that the values of both are approximately known (cf. Schmid). It is also shown that the bands are most probably of the type Π1Π1, but possibly Σ1Σ1 or (much less likely) Σ2Σ2 or some other type. If Σ2Σ2 the emitter must be CO2+, otherwise CO2. It is proposed to designate by κ the quantum number corresponding to the angular momentum of rotation of the carbon atom relative to the O atoms around the O-C-O axis. It is pointed out that in electronic bands, one expects predominantly Δκ=0. This rule is then applied to possible interpretations of the band structures. Some suggestions are also made concerning the vibrational analysis. Evidence from the values of B and ν1 is stated, which supports Smyth's interpretation of the a and c series as v1 progressions. It is suggested that the isolated bands λλ2896, 2883 may be the (0,0) band of a Π2Π2 transition of CO2+ with B and B almost equal.

  • Received 17 September 1932

DOI:https://doi.org/10.1103/PhysRev.42.364

©1932 American Physical Society

Authors & Affiliations

Robert S. Mulliken

  • Ryerson Physical Laboratory, University of Chicago

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Vol. 42, Iss. 3 — November 1932

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