INTENSITY RELATIONS IN $C_{av}$ MOLECULES

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1957

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Ohio State University

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“The electric moment, EA of a Cav type of molecule has been transformed by a contact transformation TEAT−1=EA11 T is so chosen that TH0T−1=H0=H0 TH1T−1=H11=0, II being the Hamiltonian for the molecule. The latter is tantamount to stipulating that the wave functions of H0+H1 are, to first order of approximation, those for the unperturbed Hamiltonian Ha. The matrix elements of EA have been evaluated for fundamental “parallel” vibrations, for fundamental “perpendicular” vibrations and for the pure rotation spectrum. The selection rules for the parallel type transition remain ΔJ±1.0;ΔK=0. The significant selection rules for the perpendicular type transition remain ΔJ=±1.0;ΔK=Δl=±1. Certain other transitions are allowed in this case, but they are almost certainly negligible. In all instances, the relations for the matrix elements of the electric moment consist of the usual unperturbed term plus correction terms depending in a more or less complicated manner upon the rotational quantum numbers J and K. On inspection one sees that the relations are hybrid functions showing the effect discussed by Nielsen2 and the effect discussed by Herman and Wallis3.”

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1H. Hanson, H. H. Nielsen, J. Waggoner, and W. H. Shaffer, J. Chem. Phys. (in press). 2H. H. Nielsen, Bull. de la Societe Royale des Sciences de Liege, p. 440. Nos. 6--7, (1951). 3R. C. Herman and R. F. Wallis, J. Chem. Phys., 23, 637, (1955).


Author Institution: Department of Physics and Astronomy, The Ohio State University

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